Inorg. Chem.

2010, 49, 8287–8297 8287

DOI: 10.1021/ic1008522

Effect of Five Membered Versus Six Membered Meso-Substituents on Structure

and Electronic Properties of Mg(II) Porphyrins: A Combined Experimental and
Theoretical Study
Avijit Ghosh,† Shaikh M. Mobin,† Roland Fr€ohlich,‡ Ray J. Butcher,§ Dilip K. Maity,*,|| and Mangalampalli Ravikanth*,†
†
Department of Chemistry, Indian Institute of Technology, Bombay, Powai, Mumbai 400 076, India,
‡
Organisch-Chemisches Institut, Universit€
at M€unster, Corrensstrasse 40, 48149 M€
unster, Germany,
§
Department of Chemistry, Howard University, 525 College Street Nw, Washington, D.C. 20059, and
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||
Theoretical Chemistry Section, Chemistry Group, Bhabha Atomic Research Centre, Mumbai 400085, India
Received April 29, 2010
Downloaded via UNIV OF LIVERPOOL on June 28, 2025 at 16:58:35 (UTC).

Meso-tetrasubstituted Mg(II) porphyrins containing six membered phenyl groups (MgTPP) and five membered thienyl
(MgTThP) and furyl groups (MgTFP) were synthesized and structurally characterized, and the effects of meso-
substituents on electronic properties were studied using NMR, absorption, fluorescence spectroscopy, and
electrochemical studies. Density functional theory (DFT) calculations were carried out to correlate with experimental
observations. The three Mg(II) porphyrins MgTPP, MgTThP, and MgTFP were crystallized as hexa-coordinate
systems with Mg(II) ion in the center of the porphyrin plane and having two tetrahydrofuran molecules as axial ligands.
The X-ray studies clearly showed that the meso-furyl groups adopt a conformation in which they are more in-plane with
the porphyrin plane whereas the thienyl and phenyl groups prefer an orthogonal arrangement with respect to the
porphyrin plane. This arrangement of meso-substituents with the porphyrin plane helps in the enhancement of
porphyrin π-delocalization in MgTFP compared to MgTThP and MgTPP. The differences in their structures are clearly
reflected in their spectral and electrochemical properties. The absorption and fluorescence bands experienced
bathochromic shifts on moving from six membered phenyls to five membered thienyl and furyl group, and the maximum
effects were observed for meso-tetrafuryl Mg(II) porphyrin. The electrochemical studies indicated that the gap
between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO)
decreases as we move from six membered phenyl groups to five membered thienyl and furyl groups, which explains
the bathochromic shifts observed in absorption and fluorescence bands. Results on structure and electronic properties
based on DFT studies are in agreement with experimental observations.

Introduction cence quantum yields and longer excited state lifetimes

Magnesium(II) ion is present as centrally coordinated (8-10 ns) compared to zinc porphyrins (2-2.5 ns).3 Impor-
metal in chlorophyll and bacteriochlorophyll and plays a tantly, magnesium porphyrins are easier to oxidize by over
very important role in photosynthesis.1 Because of their 250 mV because of the less electronegative magnesium.4
importance in biology, the study of magnesium containing These interesting electrochemical and photophysical proper-
porphyrinic compounds has been of long-standing interest. ties of Mg(II) porphyrins have been utilized recently to pre-
Magnesium porphyrins are fluorescent compounds bearing a pare novel porphyrin dyads5 and materials for optoelectronic
diamagnetic metal ion of ionic radius about 0.72 Å in the
porphyrin cavity.2 Although both zinc and magnesium (3) (a) Dorough, G. D.; Miller, J. R.; Huennekens, F. M. J. Am. Chem.
Soc. 1951, 73, 4315–4320. (b) Allison, J. B.; Becker, R. S. J. Chem. Phys. 1960,
porphyrins display quite similar absorption and emission 32, 1410–1417.
properties, magnesium porphyrins exhibit higher fluores- (4) Kadish, K. M.; Van Caemelbecke, E.; Royal, G. In The Porphyrin
Handbook; Kadish, K. M., Smith, K. M., Guilard, R., Eds.; Academic Press:
*To whom correspondence should be addressed. E-mail: dkmaity@barc. New York, 2000; Vol. 8, Chapter 55, pp 1-114.
gov.in (D.K.M.), [email protected] (M.R.). Fax: þ91-22-25767152 (5) (a) Zaleski, J. M.; Chang, C. K.; Leroi, G. E.; Cukier, R. I.; Nocera,
(M.R.). Phone: þ91-22 25767176 (M.R.). D. G. J. Am. Chem. Soc. 1992, 114, 3564–3465. (b) Wynne, K.; LeCours, S. J.;
(1) (a) The Photosynthetic Bacteria; Clayton, R. K., Sistrom, W. R., Eds.; Galli, C.; Therien, M. J.; Hochstrasser, R. M. J. Am. Chem. Soc. 1995, 117,
Plenum Press: New York, 1978. (b) Deisenhofer, J.; Michel, H. Science 1989, 3749–3753. (c) Li, J.; Diers, J. R.; Seth, J.; Yang, S. I.; Bocian, D. F.; Holten, D.;
245, 1463–1473. Lindsey, J. S. J. Org. Chem. 1999, 64, 9090–9100. (d) Natan, M. J.; Hoffman,
(2) (a) Greenwood, N. N.; Earnshaw, A. Chemistry of the Elements; B. M. J. Am. Chem. Soc. 1989, 111, 6468–6470. (e) Hascoat, P.; Yang, S. I.;
Pergamon: Oxford, 1984. (b) Li, F.; Gentemann, S.; Kalsbeck, W. A.; Seth, J.; Lammi, R. K.; Alley, J.; Bocian, D. F.; Lindsey, J. S.; Holten, D. Inorg. Chem.
Lindsey, J. S.; Holten, D.; Bocian, D. F. J. Mater. Chem. 1997, 7, 1245–1262. 1999, 38, 4849–4853.

r 2010 American Chemical Society Published on Web 08/20/2010 pubs.acs.org/IC

8288 Inorganic Chemistry, Vol. 49, No. 18, 2010 Ghosh et al.
device applications.6 Generally, the magnesium(II) porphyr- structure and electronic properties of tetraryl substituted
ins were prepared under harsh conditions by treating por- metalloporphyrins having six membered aryl groups versus
phyrin with MgX2 (X = Cl and Br) in refluxing dimethyl- five membered aryl groups as meso-aryl substituents. In this
formamide (DMF).7 Lindsey and co-workers8 recently paper, we report the synthesis, structure, optical, electroche-
developed simple homogeneous and heterogeneous methods mical, and fluorescence properties of Mg(II) porphyrins
at room temperature for insertion of Mg(II) ion into the having six membered phenyl groups as well as Mg(II)
porphyrin and related macrocycles. There are several reports porphyrins having five membered thienyl and furyl groups
on structurally characterized Mg(II) porphyrins where their at meso-positions. The study clearly shows that the structure
ground and excited state dynamics have been studied, but and electronic properties of Mg(II) porphyrins are greatly
these reports are restricted to Mg(II) porphyrins having six altered on changing six membered meso-phenyls with five
membered aryl groups such as phenyls or substituted phenyls membered meso-thienyls or meso-furyls, and maximum ef-
or pyridyls at meso-positions.9 Recently, we and others have fects were observed with Mg(II) porphyrin having five
synthesized meso-aryl porphyrins having five membered aryl membered furyl groups at meso-positions. To support the
groups such as furyls, thienyls, pyrazolyls, imidazoles, pyr- inferences drawn based on experimental results and to pro-
rolyls, or azulenyls at meso-positions.10 The limited studies vide more insight into the effect of substituents on electronic
available in the literature clearly showed that the electronic properties of these Mg(II) porphyrins, quantum chemical
properties of the porphyrin ring are greatly altered when six calculations were carried out applying density functional
membered meso-aryl groups are replaced with five membered theory (DFT). Despite their immense importance in biology,
aromatic heterocycles. A perusal of the literature reveals that only a few theoretical studies on Mg-porphyrin systems have
metalloporphyrin chemistry with five membered meso-sub- been made to study electronic absorption properties of these
stituents has remained largely unexplored,11 and to the best macrocyclic systems (which are rather large for ab initio
of our knowledge, there is no systematic study on the calculations).12,13 In the present study, DFT based equilib-
rium structures in the ground (S0) state and electronic
properties in the ground as well as excited states of these
(6) (a) Ambroise, A.; Wagner, R. W.; Rao, P. D.; Riggs, J. A.; Hascoat,
P.; Diers, J. R.; Seth, J.; Lammi, R. K.; Bocian, D. F.; Holten, D.; Lindsey, three Mg(II) porphyrins are reported. UV-vis spectra of
J. S. Chem. Mater. 2001, 3, 1023–1034. (b) Wagner, R. W.; Lindsey, J. S.; Seth, these systems are simulated based on calculated excited state
J.; Palaniappan, V.; Bocian, D. F. J. Am. Chem. Soc. 1996, 118, 3996–3997. properties following Time Dependent DFT (TD-DFT). A
(7) Adler, A. D.; Longo, F. R.; Kampas, F.; Kim, J. J. Inorg. Nucl. Chem. direct correlation is observed in the shift of absorption
1970, 32, 2443–2445.
(8) (a) Lindsey, J. S.; Woodford, J. N. Inorg. Chem. 1995, 34, 1063–1069. maxima (λmax) between the experimental and theoretical
(b) O'Shea, D. F.; Miller, M. A.; Matsueda, H.; Lindsey, J. S. Inorg. Chem. 1996, values especially in the Soret band region. Contour plots of
35, 7325–7338. frontier orbitals are generated to assign the type of electronic
(9) (a) Timkovich, R.; Tulinsky, A. J. Am. Chem. Soc. 1969, 91, 4430–
4432. (b) Byrn, M. P.; Curtis, C. J.; Hsiou, Y.; Khan, S. I.; Sawin, P. A.; Tendick,
transitions involved. Energy gaps between the highest occu-
S. K.; Terzis, A.; Strouse, C. E. J. Am. Chem. Soc. 1993, 115, 9480–9491. (c) pied molecular orbital (HOMO) and the lowest unoccupied
Collins, D. M.; Hoard, J. L. J. Am. Chem. Soc. 1970, 92, 3761–3771. (d) Storm, molecular orbital (LUMO) are also calculated to see the
C. B.; Corwin, A. H.; Arellano, R. R.; Martz, M.; Weintraub, R. J. Am. Chem. effect of substituents in tuning the energy gaps in these Mg(II)
Soc. 1966, 88, 2525–2531. (e) Fuhrhop, J.-H.; Mauzerall, D. J. Am. Chem. Soc.
1969, 91, 4174–4181. (f) Proni, G.; Pescitelli, G.; Huang, X.; Nakanishi, K.;
porphyrinic systems and correlated with the experimental
Berova, N. J. Am. Chem. Soc. 2003, 125, 12914–12927. (g) Lintuluoto, J. M.; results based on electrochemical studies. Again, a very good
Borovkov, V. V.; Inoue, Y. J. Am. Chem. Soc. 2002, 124, 13676–13677. (h) Berg, correlation is achieved between the experimental and the
A.; Rachamim, M.; Galili, T.; Levanon, H. J. Phys. Chem. 1996, 100, 8791– theoretical values of energy gaps.
8795. (i) Kadish, K. M.; Shiue, L. R. Inorg. Chem. 1982, 21, 1112–1115. (j)
Mckee, V.; Rodley, C. A. Inorg. Chim. Acta 1988, 151, 233–236. (k) Barkigia,
K. M.; Spaulding, L. D.; Fajer, J. Inorg. Chem. 1983, 22, 349–351. (l) Hibbs, W.; Results and Discussion
Arif, A. M.; Botoshansky, M.; Kaftory, M.; Miller, J. S. Inorg. Chem. 2003, 42,
2311–2322. (m) McKee, V.; Ong, C. C.; Rodley, G. A. Inorg. Chem. 1984, 23, There are several methods available to synthesize Mg(II)
4242–4248. (n) Szulbinski, W. S. Inorg. Chim. Acta 1995, 228, 243–250. (o) porphyrins. However the approach adopted by Lindsey et
Osuka, A.; Marumo, S.; Taniguchi, S.; Okada, T.; Mataga, N. Chem. Phys. Lett. al.,8 is very simple and gives Mg(II) porphyrins in high yield.
1994, 230, 144–148. (p) Loewe, R. S.; Lammi, R. K.; Diers, J. R.; Kirmaier, C.; We adopted Lindsey’s homogeneous approach8a to synthe-
Bocian, D. F.; Holten, D.; Lindsey, J. S. J. Mater. Chem. 2002, 12, 1530–1552.
(q) El-Khouly, M. E.; Araki, Y.; Ito, O.; Gadde, S.; McCarty, A. L.; Karr, P. A.; size MgTPP and MgTFP (Scheme 1). According to Lindsey’s
Zandlerb, M. E.; D'Souza, F. Phys. Chem. Chem. Phys. 2005, 7, 3163–3171. (r) approach, we reacted the corresponding free base porphyrin
Bonnett, R.; Hursthouse, M. B.; Malik, K. M. A.; Mateen, B. J. Chem. Soc., in CH2Cl2 with MgBr2 3 O(Et)2 for 15 min at room tempera-
Perkin Trans. 2 1977, 2072–2076. (s) Atefi, F.; McMurtrie, J. C.; Arnold, D. P. ture. The reaction progress was monitored by UV-visible
Dalton Trans. 2007, 2163–2170.
(10) (a) Gupta, I.; Ravikanth, M. Tetrahedron 2003, 59, 6131–6139. (b) spectroscopy. Interestingly, the method worked well only for
Guo, C. C.; Ren, T. G.; Wang, J.; Li, C. Y.; Song, J. X. J. Porphyrins the synthesis of MgTPP and MgTFP (Scheme 1) but did not
Phthalocyanines 2005, 9, 430–436. (c) Bhaumik, J.; Yao, Z.; Borbas, K. E.; work for MgTThP. We used the conventional approach to
Taniguchi, M.; Lindsey, J. S. J. Org. Chem. 2006, 71, 8807–8817. (d) Gupta, I.; synthesize MgTThP by refluxing H2TThP with excess MgCl2
Ravikanth, M. J. Photochem. Photobiol. A: (Chem). 2006, 177, 156–163. (e)
Kurotobi, K.; Osuka, A. Org. Lett. 2005, 7, 1055–1058. (f) Furuta, H.; Maeda, in DMF7 (Scheme 1). The compounds MgTPP, MgTThP,
H.; Osuka, A. Org. Lett. 2000, 2, 187–189. (g) Brueckner, C.; Foss, P. C. D.; and MgTFP were purified by alumina column chromatog-
Sullivan, J. O.; Pelto, R.; Zeller, M.; Birge, R. R.; Crundwell, G. Phys. Chem. raphy and recrystallized from tetrahydrofuran (THF). The
Chem. Phys. 2006, 8, 2402–2412. (h) Santosh, G.; Ravikanth, M. Chem. Phys. formation of Mg(II) porphyrins was confirmed by observa-
Lett. 2007, 448, 248–252. (i) Santosh, G.; Ravikanth, M. Tetrahedron 2007, 63,
7833–7844. tion of a molecular ion peak in the mass spectra. The
(11) (a) Rochford, J.; Botchway, S.; McGarvey, J. J.; Rooney, A. D.; Pryce, structures of Mg(II) porphyrins were determined by X-ray
M. T. J. Phys.Chem. A 2008, 112, 11611–11618. (b) Boyle, N. M.; Rochford, J.;
Pryce, M. T. Coord. Chem. Rev. 2010, 254, 77–102. (c) Purushothaman, B.;
Varghese, B.; Bhyrappa, P. Acta Crystallogr. Sect. C: Cryst. Struct. Commun. (12) Sundholm, D. Chem. Phys. Lett. 2000, 317, 392–399.
2001, C57, 252–253. (13) Rubio, M.; Roos, B. O. J. Chem. Phys. 1999, 110, 7202–7209.
Article Inorganic Chemistry, Vol. 49, No. 18, 2010 8289
Scheme 1. Synthesis of Mg(II) Porphyrins [MgTPP, MgTThP, and out of plane displacement of the central Mg(II) ion and
MgTFP] porphyrin nonplanarity is also neligible in all three cases.
However, the four pyrrole rings are not coplanar and
deviate alternately up and down from the mean plane giving
a wave-like conformation. The deviation of pyrrole rings
from the mean plane of the four meso-carbons of porphyrin
helps in the decrease of dihedral angle between porphyrin
plane and meso-substituents which in turn leads to strong
electronic interaction between the porphyrin ring and meso-
substituents. In Mg(II)TPP(THF)2, Mg(II)TThP(THF)2,
and Mg(II)TFP(THF)2, pyrroles A/C and B/D deviate by
8.01°/5.05°, 7.16°/5.51°, and 9.74°/5.10°, respectively.
A close inspection of structures of Mg(II) porphyrins
indicates that in the case of MgTPP and MgTThP, one set
of trans meso-aryl groups are almost perpendicular to the
plane of the porphyrin (99.3° and 87.5°, respectively)
whereas the dihedral angle for the other set of meso-aryl
groups is considerably reduced (57.1° and 58.2°, re-
spectively). For MgTFP, on the other hand, not only is
the average dihedral angle much smaller than those for
both MgTPP and MgTThP but both dihedral angles have
similar values (46.3° and 50.8°). This reduced dihedral
angle indicates that there is more coplanarity between the
meso-furyl groups and the porphyrin plane in Mg(II)-
crystallography, and the electronic properties were studied by TFP(THF)2 which helps in the enhancement of π-con-
spectroscopic and electrochemical techniques. jugation resulting in the observed alteration of its electro-
Crystallographic Characterization of MgTPP, MgTThP, nic properties. This is also clearly reflected in several bond
and MgTFP. All three molecules were crystallized via slow distances such as CR-Cβ, Cβ-Cβ, Cm-Cma, and so forth
diffusion of n-hexane into the THF solutions of Mg(II) (Figure 2 and Table 2), which are shorter for Mg(II)TFP-
porphyrins over a period of one week. The compounds (THF)2 as compared with the other two Mg(II) porphyr-
MgTPP and MgTThP were crystallized in the triclinic space ins (Table 2). Furthermore, the axial THF ligands are
group P1 whereas MgTFP was crystallized in the mono- involved in steric interaction with meso-substituents in
clinic space group P21/c. The crystal data and data collec- Mg(II)TPP(THF)2 and Mg(II)TThP(THF)2; hence the
tion parameters are given in Table 1, and comparisons axial ligands in these two Mg(II) porphyrins are distorted
of selected bond distances and bond angles of MgTPP, unlike in Mg(II)TFP(THF)2. This can be due to the ortho-
MgTThP, and MgTFP are given in Table 2. A comparison gonal arrangement of meso-aryl groups with respect to
of perspective views of MgTPP, MgTThP, and MgTFP is porphyrin plane in MgTPP and MgTThP which causes
shown in Figure 1. All three Mg(II) porphyrin complexes the steric hindrance leading to distortion of THF ligands.
exhibit hexa-coordinated octahedral geometry with two However, in MgTFP, the meso-furyl groups are more
tetrahydrofuran molecules bonded to Mg(II) ion as fifth coplanar with the porphyrin leading to less steric hindrance
and sixth ligands (hence these complexes are represented as between axial THF ligands and meso-furyl groups. This is
Mg(II)P(THF)2, where P = TPP, TThP, and TFP). Mag- also reflected in the bond distance between Mg(II) ion and
nesium porphyrins may crystallize either in five-coordinated axial “O” of tetrahydrofuran which is longer for Mg(II)-
or six-coordinated geometric fashion depending on the TPP(THF)2 and Mg(II)TThP(THF)2 (by ∼0.05 Å) and
nature of the solvent used for the crystallization.9a,j,k,m,14 shorter for Mg(II)TFP(THF)2 supporting the observation
In five-coordinated entities, the magnesium atom is dis- that the axial ligands can approach Mg(II) ion more closely
placed out of the mean plane of the four pyrrole nitogen in Mg(II)TFP(THF)2 because of the equivalent conforma-
atoms toward the axial ligands, by values ranging from tion adopted by its meso-furyl substituents. The binding
0.027 to 0.496 Å, whereas this out-of-plane displacement of properties of central metal ion in these Mg(II) porphyrin
central magnesium atom is negligible in six coordinated complexes are quite different compared to transition metal
cases. In all three Mg(II) porphyrins the central Mg(II) ion porphyrin complexes. For the Fe(II)TPP(THF)2 com-
is perfectly in the plane defined by four meso-carbons as it is plex,15 which is quite similar to Mg(II)TPP(THF)2, the
located on a crystallographic center of inversion. A compar- average M;N bond lengths are quite comparable with
ison of the structures and geometrical features of all com- Mg(II)TPP(THF)2 but the M;O distance is considerably
plexes is shown in Table 3, and it is clear that there is no longer by ∼0.11 Å. This indicates that the axial THF
molecules are loosely bound to Fe(II)TPP(THF)2 complex
compared to Mg(II)TFP(THF)2 where the M;O distance
(14) (a) Fischer, M. S.; Templeton, D. H.; Zalkin, A.; Calvin, M. J. Am. is shorter and indicates that the axial THF ligand is strongly
Chem. Soc. 1971, 93, 2622–2628. (b) Chow, H. C.; Serlin, R.; Strouse, C. E. coordinated to the oxo-philic Mg(II) ion.
J. Am. Chem. Soc. 1975, 97, 7230–7237. (c) Serlin, R.; Chow, H. C.; Strouse,
C. E. J. Am. Chem. Soc. 1975, 97, 7237–7242. (d) Kratky, C.; Dunitz, J. D. Acta
Crystallogr., Sect. B: Struct. Crystallogr. Cryst. Chem. 1977, B33, 545–547. (15) Barkigia, K. M.; Palacio, M.; Sun, Y.; Nogues, M.; Renner, M. W.;
(e) Kratky, C.; Isenring, H. P.; Dunitz, J. D. Acta Crystallogr., Sect. B: Struct. Varret, F.; Battioni, P.; Mansuy, D.; Fajer, J. Inorg. Chem. 2002, 41, 5647–
Crystallogr. Cryst. Chem. 1977, B33, 547–549. 5649.
8290 Inorganic Chemistry, Vol. 49, No. 18, 2010 Ghosh et al.
Table 1. Crystallographic Data for MgTPP, MgTThP, and MgTFP

parameters MgTPP MgTThP MgTFP

mol formula C48H40MgN4O2 C44H36MgN4O2S4 C44H36MgN4O6
fw 928.89 805.32 741.08
cryst sym triclinic triclinic monoclinic
space group P1 P1 P21/c
a (Å) 12.3262(18) 9.5942(7) 9.882(7)
b (Å) 12.326(3) 10.1952(7) 20.508(3)
c (Å) 13.9882(16) 11.7484(8) 9.566(4)
R (deg) 98.702(13) 66.492(3) 90
β (deg) 105.311(11) 76.053(3) 115.24
γ (deg) 95.727(14) 65.476(6) 90
V (Å3) 2004.4(6) 954.80(12) 1753.7(14)
Z 2 1 2
μ (mm-1) 0.091 2.804 0.110
Dcalcd (g cm-3) 1.267 1.401 1.403
F(000) 944 420 776
2θ range (deg) 3.08-49.96 4.12-67.82 3.02-25.00
e data (Rint) 6996/0.0327 10709/0.036 10800/0.0311
R1, wR2 [I > 2σ(I )] 0.0481, 0.1085 0.0451, 0.1207 0.0353, 0.0905
R1, wR2 (all data) 0.1292, 0.1307 0.0487, 0.1245 0.0496, 0.0935
GOF 1.013 1.041 1.030
largest diff. peak/hole, (e Å-3) 0.823 /-0.570 0.499/-0.333 0.709/-0.264

Table 2. Comparison of Some Selected Bond Length [Å] and Bond Angles [deg] systems in case of MgTFP supramolecular assembly
Obtained from Both X-ray Crystal Structure and Optimized Structure resulting in all the dihedral angles between meso-groups
X-ray structure optimized structure
and porphyrin plane being similar as shown in Figure 4
since each unit feels equal interactions.
parameter MgTPP MgTThP MgTFP MgTPP MgTThP MgTFP Spectral and Electrochemical Properties. The effect of
Mg-N1 2.073(1) 2.073(1) 2.084(2) 2.09 2.09 2.09
six membered phenyl groups versus five membered thie-
Mg-N2 2.070(1) 2.073(1) 2.077(2) 2.09 2.09 2.09 nyl and furyl groups is clearly reflected in their spectral
Mg-N3 2.073(3) 2.073(1) 2.084(2) 2.09 2.09 2.09 and electrochemical properties, and these are in agree-
Mg-N4 2.070(1) 2.073(1) 2.077(2) 2.09 2.09 2.09 ment with their crystal structures. The comparison of 1H
Mg-O 2.241(1) 2.267(2) 2.210(2) 2.28 2.27 2.27 NMR spectra of MgTPP, MgTThP, and MgTFP re-
Cm-Cmaa 1.493 1.488 1.473 1.49 1.48 1.47
corded in CDCl3 is presented in Figure 5. In all three
Cβ-Cβa 1.349 1.352 1.346 1.36 1.36 1.36
Cβ-CRa 1.442 1.444 1.444 1.44 1.44 1.44 Mg(II) porphyrins, the eight β-pyrrole protons appeared
dihedral angleb 78.2 72.8 48.5 65.9 70.3 52.9 as singlets. However, the β-pyrrole protons experien-
a
ced ∼0.2 ppm downfield shift on changing the meso-
Average bond distance (in Å). b Average dihedral angle (deg)
between porphyrin ring and meso-substituents. Cm-Cma is the average
substituent from six membered phenyl group to five
distance (Å) between meso-carbon atom and the carbon atom through membered thienyl and furyl groups, and maximum down-
which respective meso-aryl group is attached to meso-positions. field shift was observed for MgTFP. This indicates that
there is an alteration in ring current on changing the meso-
In addition to the above-mentioned differences be- substituent from six membered phenyl group to five
tween the structures of Mg(II) TFP(THF)2 and Mg(II)- membered thienyl and furyl groups. From crystal struc-
TPP(THF)2, a novel feature of Mg(II)TFP(THF)2 is the tures, it is clear that among Mg(II) porphyrins, the meso-
presence of intramolecular and intermolecular hydrogen substituents are more coplanar with the porphyrin plane
bonding interactions. The intramolecular hydrogen only in MgTFP, leading to strong interaction between
bonding as shown in the packing diagram (Figure 3) is porphyrin macrocycle and meso-furyl groups. This inter-
present between meso-furyl “O” and β-pyrrole “H” which action results in the alteration of π-conjugation which
may be assisting in the decrease of dihedral angle between results in the more downfield shift of β-pyrrole protons in
meso-furyl groups and plane of the porphyrin. In addi- MgTFP compared to MgTPP and MgTThP.
tion, the Mg(II)TFP(THF)2 also shows intermolecular Similar observations were made in the absorption
hydrogen bonding (O2 3 3 3 3 H-C14 and C14;H 3 3 3 3 O2) spectroscopy. The Q- and Soret band absorption spectra
between meso-furyl “O” (O2) of one porphyrin unit with of MgTPP, MgTThP, and MgTFP are shown in Figure 6,
“H” (H14) of meso-furyl group of second porphyrin and and absorption data are presented in Table 4. Inspection
vice versa leading to the formation of the supramolecular of Figure 6 and Table 4 reveals the following: (1) In
assembly (Figure 4). A weak hydrogen bonding is also general, all three Mg(II) porphyrins showed two Q-bands
observed between O2 of meso-furyl group and H-C8 and one strong Soret band; (2) both Soret and Q-bands
of meso-furyl group from other porphyrin unit. Thus, experienced bathochromic shifts with slight alteration in
MgTFP(THF)2 exhibits different structural properties absorption coefficients on changing six membered phenyl
than other two Mg(II) porphyrins. Note that crystal groups with five membered thienyl and furyl groups
structures have produced two different sets of dihedral at meso-positions and (3) the maximum red shifts in
angles between meso-groups and porphyrin plane in case absorption bands were observed for MgTFP compared
of MgTPP and MgTThP as the meso-groups are not to MgTThP. Thus, the absorption study supported the
involved in H-bonding. However, as it was just discussed, alteration of electronic properties of the Mg(II) porphyr-
there are H-bonds between two macrocyclic porphyrin in on changing six membered phenyl groups with five
Article Inorganic Chemistry, Vol. 49, No. 18, 2010 8291
Table 3. Selected Geometrical Parameters

MgTPP MgTFP MgTThP

Mg-Npa,b 2.072 2.080 2.073
Mg-Oaxa,b 2.241(12) 2.210(16) 2.267(16)
Δ24Mgc 0.00 0.00 0.00
Δ4NMgd 0.00 0.00 0.00
Δ24e 0.07 0.08 0.03
Cm f 0.13 0.13 0.08
Cβf 0.36 0.35 0.31
b
core size 2.072 2.080 2.073
a
Average value in Å. b Value in Å. c Displacement (in Å) of magne-
sium from the 24-atom mean plane of the porphyrin core. d Displace-
ment (in Å) of magnesium from the mean plane of the four pyrrole
nitrogen atoms. e Average displacement (in Å) of the 24 atoms of the
porphyrin macrocycle from the least-squares plane of the 24 atoms of the
porphyrin ring. f Average displacement (in Å) from four porphyrinic
nitrogen atoms.

Figure 2. Formal diagram of the Mg(II) porphyrin core displaying the

common symbol for MgTPP, MgTThP, and MgTFP; the corresponding
independent bond lengths are summarized in Table 3.

in our DFT studies of Mg(II) porphyrins which supports

more orbital overlap of meso-substituents with porphyrin
ring in MgTFP. The trends observed in the absorption
properties are in agreement with the X-ray structures of
MgTPP, MgTThP, and MgTFP.
The redox properties of three Mg(II) porphyrins were
studied by cyclic voltammetric and differential pulse
voltammetric techniques using tetrabutylammonium per-
chlorate as supporting electrolyte (0.1 M) in dichloro-
methane as solvent. A comparison of oxidation and
reduction waves of cyclic voltammograms is shown in
Figure 7, and data for all three Mg(II) porphyrin deriva-
tives are presented in Table 5. In general, metallopor-
phyrins exhibit one or two ring centered oxidations and
one or two ring centered reductions along with metal
centered oxidation and reduction in case of redox active
metal center present in the porphyrin cavity. But each of
these three compounds exhibited only one ring-centered
reduction (-1.40 V to -1.60 V) and one or two ring-
centered oxidations (0.65 to 0.80 V). MgTPP and
MgTThP exhibited two ring centered oxidations whereas
Figure 1. ORTEP diagram of compounds (a) MgTPP, (b) MgTThP, MgTFP showed only one oxidation. The central metal
and (c) MgTFP. Ellipsoids are drawn at 50% probability level. Mg(II) being redox inactive did not show any metal
centered oxidation or reduction. The oxidations and
membered thienyl and furyl groups at meso-positions. reductions were reversible or quasi-reversible (ΔEp =
These effects are attributed to the orientation of meso- 60-120 mV) except MgTFP which showed one irrever-
substituents with respect to the mean plane of the por- sible oxidation. Inspection of the redox data (Table 5)
phyrin. In MgTPP and MgTThP, the meso-substituents reveals that the first oxidation potentials were shifted to
are arranged in orthogonal fashion with respect to the more positive potential when six membered meso-phenyls
mean plane of the porphyrin resulting in the prevention of were replaced with five membered meso-thienyl groups
significant π-conjugation between porphyrin and meso- suggesting that MgTThP is harder to oxidize than
substituents. However, in MgTFP, the five membered MgTPP. However, the reduction potentials were shifted
meso-furyl groups are more in-plane with the porphyrin to less negative potential on replacement of meso-phenyl
ring resulting in efficient extension of the porphyrin groups with meso-thienyl and meso-furyl groups indicat-
π-conjugation into meso-substituents. This is also reflected ing that the MgTThP and MgTFP are easier to reduce
8292 Inorganic Chemistry, Vol. 49, No. 18, 2010 Ghosh et al.

Figure 3. Molecular packing for compound MgTFP viewed down the a axis. The weak C-H 3 3 3 3 O intramolecular interactions between C-H of pyrrole
ring and O of meso-furyl group are shown by dashed lines.

Figure 4. Supramolecular assembly through intermolecular-hydrogen bonding network (between O2 3 3 3 3 H-C14 and C14;H 3 3 3 3 O2 of meso-furyl
group from two different porphyrin unit) in MgTFP complex.

compared to MgTPP. Furthermore, the maximum ano-

dic shifts for reduction potentials were observed for
MgTFP suggesting that the MgTFP is easier to reduce
than MgTThP.
The Δredox value which gives an estimate of HOMO-
LUMO gap calculated from the difference of the first
oxidation and first reduction potential is shown for
MgTThP in Figure 8. The Δredox is decreased on changing
meso-substituents from six membered phenyl groups to
five membered thienyl groups (Table 5). The Δredox was
not calculated for MgTFP since it exhibited an irrever-
sible oxidation. The reduction of HOMO-LUMO gap
explains the large red shifts of absorption bands of
MgTThP compared to MgTPP. It is assumed that the
HOMO-LUMO is further reduced in MgTFP which
showed maximum red shifts in absorption bands com-
pared to the other two Mg(II) porphyrins.
Figure 5. Comparison of 1H NMR of compounds MgTPP, MgTThP, The fluorescence properties were studied by both
and MgTFP (* = residual CHCl3 in CDCl3). steady state and time-resolved fluorescence techniques
Article Inorganic Chemistry, Vol. 49, No. 18, 2010 8293
to understand the effect of meso-substituents on electro- were observed for MgTFP. These observations are in
nic properties of Mg(II) porphyrins in the singlet excited line with the absorption studies and support the effi-
state. The comparison of fluorescence spectra is shown in cient π-delocalization between porphyrin and meso-
Figure 9a, and the data are presented in Table 5. The substituents in MgTFP compared to MgTThP and
MgTPP and MgTThP showed two fluorescence bands MgTPP. The quantum yields calculated by comparative
and MgTFP showed one broad fluorescence band. The method showed the following trend: MgTPP > MgTFP
inspection of Figure 9a and data presented in Table 5 >MgTThP. The low quantum yield of MgTThP was due
reveal that the fluorescence bands experienced red shifts to the presence of heavy sulfur atoms of meso-thienyl
on changing meso-phenyl substituents to meso-thienyl groups which enhances the non-radiative pathways and
and meso-furyl substituents, and maximum red shifts reduces the fluorescence yield. The singlet excited state
lifetime was measured by single-photon counting techni-
que. The Mg(II) porphyrins were excited at 406 nm, and
emissions were detected at emission peak maxima of the
corresponding Mg(II) porphyrin. The fluorescence decay
of Mg(II) porphyrins was fitted to a single exponential,
and the representative fluorescence decay profiles of
MgTPP, MgTThP, and MgTFP along with residual fits
are shown in Figure 9b and 9c, respectively. The singlet
excited state lifetime τf of Mg(II) porphyrins is in agree-
ment with their corresponding quantum yield, and the
low singlet state lifetime observed for MgTThP is due to
the presence of heavy sulfur atoms. Thus, the singlet state
excited properties support the alteration of electronic
properties on replacement of six membered meso-phenyl
groups with five membered meso-thienyl and meso-furyl
groups in Mg(II) porphyrins.
Quantum Chemical Studies. Minimum energy struc-
tures of three metalloporphyrins MgTPP, MgTThP,
and MgTFP calculated at B3LYP/6-31G(d) level of
theory are displayed in Figure 10. This choice of DFT
functional and basis set should be adequate for metallo-
porphyrin systems. Selected bond lengths and torsion
angles have been provided in Table 2 along with the
X-ray crystallographic data for comparison. To bring
about the direct correlation between calculated and
experimentally observed properties, the equilibrium
Figure 6. Comparison of normalized absorption spectra of MgTPP
(dotted lines), MgTThP (dashed lines) and MgTFP (solid lines), recorded
in toluene, (a) Soret band and (b) Q-band.

Table 4. 1H NMR Data and Absorption Data

1
H NMR a absorption data b

δ in ppm Soret band

compound β-pyrrole λ (nm) (logε) Q-bands λ (nm) (log ε)
MgTPP 8.85 (s, 8 H) 426 (5.75) 524 (sh), 564 (4.25), 604 (3.95)
MgTThP 9.02 (s, 8 H) 433 (5.74) 530 (sh), 570 (4.28), 613 (3.79)
MgTFP 9.10 (s, 8 H) 437 (5.56) 532 (sh), 572 (4.15), 620 (3.87)
Figure 7. Comparison of oxidation and reduction waves of cyclic
a
All spectra recorded in CDCl3. b All spectra recorded in toluene; the voltammograms (scan rate =50 mV s-1) of MgTPP, MgTThP, and
concentration used for Q-band spectra was ∼5  10-5 M and for Soret MgTFP in CH2Cl2 containing 0.1 M tetrabutylammonium perchlorate
band was ∼5  10-7 M, sh = shoulder. (TBAP) as supporting electrolyte.

Table 5. Redox Potential Data and Emission Data

redox dataa (V)

oxidation reduction emission datab

compound I II I HOMO-LUMO gap (Δredox) Q (0, 0) (nm) Q (0, 1) (nm) Φf τf (ns)

MgTPP 0.65 0.94 -1.57 2.22 609 660 0.16 8.90
MgTThP 0.78 0.98 -1.42 2.20 626 669 0.003 0.37
MgTFP 0.68c -1.40 649 0.024 3.28
a
In CH2Cl2 solvent with 0.1 M tetrabutylammonium perchlorate (TBAP) as supporting electrolyte; scan rate =50 mV s-1. b All data were recorded in
toluene. c Irreversible.
8294 Inorganic Chemistry, Vol. 49, No. 18, 2010 Ghosh et al.

Figure 8. HOMO-LUMO gap of MgTThP.

Figure 9. (a) Comparison of normalized emission spectra of MgTPP

(solid lines), MgTThP (dotted lines), and MgTFP (dashed lines) recorded
in toluene, (b) fluorescence decay profile, and (c) the weighted residuals
distribution fit of fluorescence decays of MgTPP, MgTThP, and MgTFP.
The excitation wavelength used was 406 nm, and emissions were detected
at different wavelengths depending on the emission peak maxima of the
corresponding meso-tetrasubstituted Mg(II) porphyrins. Figure 10. Fully optimized structures of (a) MgTPP, (b) MgTThP, and
(c) MgTFP applying B3LYP/6-31G(d) level of theory (numbering of
structures are optimized keeping two THF solvent mole- atoms for each complex has been shown following the corresponding
cules in the axial positions similar to crystal structures crystal structure).
obtained for these Mg(II) porphyrins. It is observed that
such geometrical arrangement leads to the most stable In fact, a few optimizations are carried out taking such
structure in the ground (S0) state when full geometry possible structures as the starting geometry which leads to
optimization is carried out applying the Newton- a less stable structure. The cavity size of MgTPP and
Raphson procedure. The possibility of other conformers MgTThP is ∼4.177 Å, and for MgTFP it is 4.188 Å. These
does exist, for example, in the case of MgTFP, the meso- values are close to the size obtained from crystal structure
furyl group can be arranged in all possible orientations determination. The other parameters are also in line with
with respect to the heteroatom oxygen because of possible crystallographically obtained data as displayed in Table 2.
allowed rotation through the single bond between the It is worth mentioning that theoretical calculations are
meso-carbon atom and the carbon atom through which carried out under isolated condition, and this leads to
meso-furyl group is attached to the porphyrin unit. only one set of dihedral angles between meso-substituents
Article Inorganic Chemistry, Vol. 49, No. 18, 2010 8295
and porphyrin plane in each case as there are no inter- tively. By scrutinizing the energy values of the HOMO
molecular interactions unlike in crystals. It is to be noted and LUMO of all three complexes, it is inferred that in
that the average dihedral angle between the meso-substit- the case of MgTFP, the HOMO and LUMO are stabi-
uents and mean porphyrin ring are ∼70° in MgTPP, and lized by 0.115 and 0.258 eV, respectively, as compared to
in MgTThP and ∼53° in MgTFP. This indicates that MgTThP. Similarly, in case of MgTThP, HOMO and
meso-furyl group is more inclined toward porphyrin ring LUMO are stabilized by 0.157 and 0.180 eV respectively
compared to meso-phenyl and meso-thienyl groups. relative to MgTPP. The HOMO-LUMO gaps calculated
Frontier molecular orbitals (FMO) are also calculated from these HOMO-LUMO energies follow the same
and displayed in Figure 11. This figure suggests more trend (MgTPP >MgTThP >MgTFP) as obtained from
electronic delocalization in case of MgTFP, and the meso- cyclic voltammetry redox potential values. The substan-
furyl groups are involved in FMOs (HOMOs and LUMOs) tial decrease of energy gap between HOMO and LUMO
to bring down the orbital energy through extensive from MgTPP to MgTFP via MgTThP results in red shift
π conjugation. In the case of MgTPP, there is least invol- in UV-vis spectra.
vement of meso-substituent orbitals in forming FMOs. The Vertical electronic transitions are calculated for these
energies of HOMOs follow the order as MgTPP > three metalloporphyrins applying the B3LYP functional
MgTThP > MgTFP, and a similar trend is also observed under the TD-DFT formalism with the ground state (S0)
in the case of the LUMO energy. This feature is clearly seen optimized structures predicted at the B3LYP level of
from the orbital correlation diagram as shown in Figure 11 theory. The COSMO model is also applied for accounting
with FMOs and corresponding energies of their respective for the macroscopic solvent effect in the dichloromethane
porphyrin units. It is to be noted that neither the axial solvent. Results on a few low lying electronic transtions in
coordinating solvent molecule nor the central metal parti- the Soret band region are supplied in Table 6 showing the
cipates in either of the FMOs. major electronic transitions involved in the observed
The FMO correlation diagram indicates that meso- Soret bands of these systems. As it is shown in Table 6,
substituents constitute a part of conjugated macrocycle the strong electronic transitions having oscillator strength
showing π overlap with the respective meso-substituents f >1.2 are initiated from HOMO-1 orbital in all the three
in both HOMOs and LUMOs. The energies of HOMOs cases. Note that mainly pyrrole π electrons have partici-
for MgTPP, MgTThP, and MgTFP are -4.492 eV, pated in the HOMO-1 orbital. The major electronic
-4.649 eV, and -4.764 eV, respectively. Similarly, the transitions occur to either LUMO or LUMOþ1 orbital
energies of LUMOs are -1.799 eV, -1.979 eV, and in all these systems. In both these molecular orbitals,
-2.237 eV for MgTPP, MgTThP, and MgTFP, respec- mainly porphyrin ring π* electrons participate with a
small contribution from one set of trans meso-substitu-
tents. UV-vis spectra of these three metalloporphyrins in
the Soret band region are simulated following a Gaussian
model, and the spectra are depicted in Figure 12. The
actual absorption maxima (λmax) do not agree closely
with calculated values. However, it is the order of values
that is comparable.

Conclusions
The influence of six membered versus five membered meso-
substituents on structure, spectral, and redox properties
of Mg(II) derivatives of meso-tetrasubstituted porphyrins
was described using both experimental and theoretical ap-
proaches. The crystallographic study showed that the meso-
furyl groups in MgTFP adopt a more in-plane arrangement
with the porphyrin whereas the meso-phenyls in MgTPP and
meso-thienyls in MgTThP are in out-of-plane arrangement
with the porphyrin. This indicates that in MgTFP, there is a
Figure 11. Orbital-correlation diagram of HOMO and LUMO (FMOs) greater resonance interaction between meso-furyl groups and
for MgTPP, MgTThP, and MgTFP. porphyrin ring leading to extension of π-conjugation whereas

Table 6. Vertical Transition Maxima (in nm) and Oscillator Strengths of Electronic Transitions in the Soret Band Region As Predicted by TD-DFT (B3LYP) Method
Employing 6-31G(d) Basis Set in MgTPP, MgTThP and MgTFP

system dominant transitions transition maxima (nm) oscillator strengths

MgTPP HOMO-1fLUMOþ1 (49%), HOMOfLUMO (15%) 402.5 1.3137
HOMO-1fLUMO (47%), HOMOfLUMOþ1 (17%) 401.9 1.3419
HOMO-3fLUMO (49%), HOMO-4fLUMOþ1 (21%), HOMO-3fLUMOþ1 (14%) 349.4 0.0001
MgTThP HOMO-1fLUMOþ1 (45%), HOMOfLUMO (17%) 412.8 1.2487
HOMO-1fLUMO (44%), HOMOfLUMOþ1 (18%) 411.6 1.2656
HOMO-2fLUMO (51%), HOMO-2fLUMOþ1 (33%) 364.6 0.0001
MgTFP HOMO-1fLUMOþ1 (36%), HOMO-1fLUMO (17%) 421.4 1.2205
HOMO-1fLUMO (35%), HOMO-1fLUMOþ1 (18%) 420.0 1.2204
HOMO-2fLUMO (46%), HOMO-2fLUMOþ1 (28%), HOMO-3fLUMO (13%) 388.3 0.0000
8296 Inorganic Chemistry, Vol. 49, No. 18, 2010 Ghosh et al.
X-ray Crystallography. Suitable single crystals were grown by
slow diffusion of n-hexane into the THF solution of correspond-
ing Mg(II)porphyrins. Single crystal X-ray structural studies
of MgTPP and MgTFP were performed on a CCD Oxford
Diffraction XCALIBUR-S diffractometer equipped with an
Oxford Instruments low-temperature attachment. Data were
collected at 293(2) K (in case of MgTPP) and 120(2) K (in case of
MgTFP) using graphite-monochromoated Mo KR radiation
(λR =0.71073 Å). The strategy for the data collection was eva-
luated by using the CrysAlisPro CCD software. The data were
collected by the standard j-ω scan techniques, and were scaled
and reduced using the CrysAlisPro RED software. The struc-
tures were solved by the direct method using SHELXS-9717 and
refined by full matrix least-squares with SHELXL-97, refining
on F2. The positions of all the atoms were obtained by direct
method. All non-hydrogen atoms were refined anisotropically.
Figure 12. Simulated UV-vis spectra of MgTPP, MgTThP, and
MgTFP in the Soret band region. Simulation of these absorption profiles
The hydrogen atoms were placed in geometrically constrained
was carried out from 10 low lying vertical excited states with Gaussian line positions and refined with isotropic temperature factor, gener-
shape. ally 1.2Ueq of their parent atoms. The data set for complex
MgTThP was collected with a Nonius KappaCCD diffract-
in MgTPP and MgTThP, the interaction between meso- ometer, equipped with a rotating anode generator at 223(2) K.
substituents and porphyrin ring is less. The DFT studies also Programs used: data collection COLLECT (Nonius B.V., 1998),
support strong interaction between meso-substituents and data reduction Denzo-SMN,18 absorption correction Denzo,19
porphyrin ring in MgTFP. The spectral and electrochemical structure solution SHELXS-97,20 structure refinement SHELXL-
studies are in agreement with the crystallographic studies. 97,17 graphics SCHAKAL (E. Keller, 1997).
In the case of MgTPP one of the carbon atoms (C3) of the
The absorption and fluorescence bands are shifted to the red
axial THF was disordered over two conformations with occu-
on changing the meso-substituent from six membered phenyl pancy factors of 0.64(1) and 0.36(1). In MgTThP both indepen-
groups to five membered thienyl and furyl groups, and dent thiophene molecules in the asymmetric unit are disordered,
maximum effects were observed for meso-tetrafuryl Mg(II) they were refined with split positions to resulting occupancies of
porphyrins. The electrochemical studies indicated a decrease 0.896(3):0.104(3) and 0.646(2):0.354(2), respectively. Geometri-
of HOMO-LUMO gap on changing meso-substituents from cal (SAME = same geometry, SAME is used as a relative weak
six membered phenyl groups to five membered thienyl and restraint making all bond lengths in two parts of a molecule
furyl groups, and maximum decrease was noted for MgTFP equal within a given standard deviation), and thermal (EADP =
which is in agreement with the large red shifts in absorption equal anisotropic displacement parameters) restraints were
applied for the minor components.
and fluorescence bands observed for MgTFP. Thus, it is
Theoretical Methods. DFT calculations were carried out on
concluded that by changing the meso-substituent from six
three Mg(II) porphyrin systems, namely, MgTPP, MgTThP,
membered aryl group to five membered aryl group, the and MgTFP to find out minimum energy structures and to study
electronic and structural properties of Mg(II) porphyrins their electronic properties. Searches for these structures were
can be tuned. performed in the ground electronic state (S0) applying Becke’s
three parameters correlated hybrid density functional, B3LYP
Experimental Section adopting 6-31G(d) atomic basis functions which includes at
All general chemicals and solvents were procured from least 3200 primitive Gaussian functions in total. Equilibrium
S.D. Fine Chemicals, India. Column chromatography was structures of these systems were calculated based on full geo-
performed using silica gel and basic alumina obtained from metry optimization following the Newton-Raphson proce-
Sisco Research Laboratories, India. MgBr2 3 O(Et)2 was pur- dure. Excited state calculations were carried out applying the
chased from Acros and used without further purifications. TD-DFT procedure with the B3LYP functional for 10 low lying
Tetrabutylammonium perchlorate was purchased from Fluka vertical electronic transitions on the S0 state optimized structure
and used without further purifications. using the COSMO solvation model to account for the solvent
1
H NMR spectra were recorded with Varian 400 MHz (CH2Cl2) effect with the same set of basis functions. Simulation
instrument using tetramethylsilane as an internal standard. of absorption profiles was carried out from 10 low lying excited
All NMR measurements were carried out at room tempera- states with Gaussian line shape, that is,
!
ture in deuterochloroform. Absorption and steady state X fi ðE - Ei Þ2
fluorescence spectra were obtained with Perkin-Elmer εðEÞ ¼ A exp B
Lambda-35 and Lambda-55 instruments, respectively. The i
Δi Δ2i
fluorescence quantum yields (Φf) of Mg(II) porphyrins were
estimated from the emission and absorption spectra by com- where, ε, Ε, f, Δ are molar extinction coefficient, transition
parative method.16 ES-MS spectra were recorded with a energy, oscillator strength, and half bandwidth, respectively.
Q-Tof Micromass spectrometer. Cyclic voltammetric (CV) UV-vis spectra were generated by considering the full-width at
and differential pulse voltammetric (DPV) studies were car- half-maximum (fwhm) as 100 nm. The total integrated intensity
ried out with BAS electrochemical system utilizing the three under the absorption profile was kept equal to the sum of all the
electrode configuration consisting of a glassy carbon (working
electrode), platinum wire (auxiliary electrode), and saturated (17) Sheldrick, G. M. Acta Crystallogr. 2008, A64, 112-122; SHELX,
calomel (reference electrode) electrodes in dry dichloro- Program for Crystal Structure Solution and Refinement, University of Goettingen,
methane using 0.1 M tetrabutylammonium perchlorate as Germany, 1997.
supporting electrolyte. (18) Otwinowski, Z.; Minor, W. Methods Enzymol. 1997, 276, 307–326.
(19) Otwinowski, Z.; Borek, D.; Majewski, W.; Minor, W. Acta Crystal-
logr. 2003, A59, 228–234.
(16) Gupta, I.; Ravikanth, M. Inorg. Chem. Acta 2007, 360, 1731–1742. (20) Sheldrick, G. M. Acta Crystallogr. 1990, A46, 467–473.
Article Inorganic Chemistry, Vol. 49, No. 18, 2010 8297
oscillator strengths. All the electronic structure calculations to remove the residual H2TThP. Elution with CH2Cl2/acetone
were carried out applying GAMESS suite of ab initio pro- (1: 1) afforded the desired MgTThP as dark blue solid in 91%
gram.21 Visualization of molecular structures and orbital con- yield (94 mg). Mp >300 °C. 1H NMR (400 MHz, CDCl3, 298
tour plots were carried out using the Molden visualization K): δ 9.02 (s, 8H, β-pyrrole), 7.85 (br s, 4H, R-H, meso-thienyl),
software.22 7.80 (d, 4H, β-H, meso-thienyl), 7.44-7.49 (m, 4H, β-H, meso-
General Synthesis. The magnesium complexes of porphyrins thienyl) ppm. ES-MS: C36H20N4S4Mg calcd avg mass 660.1,
were prepared according to literature procedure. There are obsd m/z 661.3 [Mþ1]þ.
several methods available for magnesium insertion into the MgTFP Complex. A 100 mg portion (0.174 mmol) of H2TFP
porphyrin cavity. We followed the most useful Lindsey’s was dissolved in 8 mL of CH2C12 in a one-neck round-bottom
method8a which produces the desired complexes in very good flask. Then 0.485 mL (3.48 mmol) of triethylamine was added
yield in case of MgTPP and MgTFP. But to synthesize MgTThP, followed by 449 mg (1.74 mmol) of MgBr2 3 O(Et)2. The reaction
we had to follow conventional route where H2TThP and MgCl2 mixture was stirred magnetically at room temperature for 15
were refluxed in DMF.7 min. The progress of complete metalation was judged by
Synthesis of MgII Derivatives of TPP, TThP and TFP. absorption spectroscopy. Then about 25 mL of CH2C12 was
MgTPP Complex. MgTPP was synthesized by following Lind- added into the reaction mixture, washed with 5% NaHCO3,
sey’s method8a reported in literature. Mp > 300 °C. 1H NMR dried (over Na2SO4), and filtered, and the filtrate was concen-
(400 MHz, CDCl3, 298 K): δ 8.85 (s, 8H, β-pyrrole), 8.21 (br s, trated to 4-5 mL. Chromatography on an alumina column
8H, o-H, meso-phenyl), 7.74 (br s, 12 H, m-, p-H, meso-phenyl) (packed in CH2Cl2 containing 0.1% triethylamine) with
ppm. ES-MS: C44H28N4Mg calcd avg mass 636.2, obsd m/z CH2C12 elution yielded unreacted H2TFP. Repeat column
637.2 [Mþ1]þ. chromatography always yields some free base H2TFP. Desired
MgTThP Complex. A sample of 100 mg (0.157 mmol) of compound was collected as a purple-green fraction by elution
H2TThP was dissolved in 100 mL of DMF in a one-neck round- with CH2Cl2/acetone (1: 1). These fractions were evaporated to
bottom flask. Then 320 mg (1.57 mmol) of MgCl2 3 6H2O was dryness, and the crude solid compound was recrystallized with
added into that solution. The mixture was then refluxed over- n-hexanes affording dark green solid. Yields: 96 mg (93%). Mp
night. The solution became greenish pink in color. The solvent >300 °C. 1H NMR (400 MHz, CDCl3, 298 K): δ 9.10 (s, 8H, β-
was removed completely to dryness under reduced pressure. The pyrrole), 8.05(s, 4H, R-H, meso-furyl), 7.20 (br s, 4H, β-H, meso-
solid obtained was loaded onto an alumina column packed in furyl), 7.00 (br s, 4H, β-H, meso-furyl) ppm. ES-MS: C36H20-
CH2Cl2 containing 0.1% triethylamine and eluted with CH2C12 N4O4Mg calcd avg mass 596.1, obsd m/z 597.2 [Mþ1]þ.

(21) Schmidt, M. W.; Baldridge, K. K.; Boatz, J. A.; Elbert, S. T.;

Gordon, M. S.; Jensen, J. H.; Koseki, S.; Matsunaga, N.; Nguyen, K. A.;
Acknowledgment. M.R. thanks CSIR and DST for financial
Su, S. J.; Windus, T. L.; Dupuis, M.; Montgomery, J. A. J. Comput. Chem. support, and A.G. thanks IIT-Bombay for a fellowship. Com-
1993, 14, 1347–1363. puter Centre, BARC is gratefully acknowledged for generous
(22) Schaftenaar, G.; Noordik, J. H. J. Comput.-Aided Mol. Des. 2000, 14, CPU time in ANUPAM parallel computer systems. Authors
123–134. also thank Mr. Ranjan Patra for his help.