Abstract
We report the first band structure calculations of the quasi-one-dimensional [MnTPP][TCNE] compounds (TPP = meso-tetraphenylporphyrinato, TCNE = tetracyanoethylene), based on Density Functional Theory (DFT) methods, in order to interpret the magnetic ordering in these prototypic systems. We compare and contrast the results of broken-symmetry DFT calculations for extended systems, with periodic boundary conditions, and for finite systems, magnetic dimers modeling the actual molecular magnets. By varying systematically the main angles, we are able to determine the geometry dependence of the exchange interaction. Structure–properties correlations in these charge-transfer salts reveal the determinant role of the Mn-(N≡C)TCNE bond angle on the strength of the ferrimagnetic coupling between the S 1 = 2 spin located on the MnIII-porphyrin donor and the S 2 = 1/2 spin positioned on the cyanocarbon acceptor. When the Mn-(N≡C)TCNE angle is decreased, the intrachain magnetic coupling strengthens, correlated with the increase in the \( d_{{z^{2} }} - \pi * \) orbital overlap. The exchange coupling constants resulting from DFT calculations of extended systems, with periodic boundary conditions, were found to be consistent with those obtained for the dimers, but systematically smaller. The exchange constants vary strongly with the functional used, hybrid functionals such as B3LYP leading to results that better correlate with the experimental mean-field critical temperatures. The coupling constant varies significantly with the type of broken-symmetry approach, depending on the overlap between magnetic orbitals, but weakly on the basis set once polarization effects are included. The electronic structure calculations for the extended systems provide a density of states consistent with the energy spectrum of the corresponding dimer, allowing for an intuitive explanation of the intrachain ferrimagnetic ordering.
Similar content being viewed by others
References
Kahn O (1993) Molecular magnetism. VCH Publishers, New York
Miller JS, Drillon M (eds) (2002) Magnetism: molecules to materials. Wiley-VCH, Weinheim
Gîrţu MA, Fahlman M (2009) In: Nalwa HS (ed) Magnetic nanostructures, hybrid organic-inorganic nanostructured magnets. American Scientific Publishers, Stevenson Ranch, pp 359–433
Miller JS, Calabrese JC, McLean RS, Epstein AJ (1992) Adv Mater 4:498
Sugiura K-I, Arif A, Rittenberg DK, Schweizer J, Ohrstrom L, Epstein AJ, Miller JS (1997) Chem Eur J 3:138
Brandon EJ, Sugiura K-I, Arif AM, Liable-Sands A, Rheingold AL, Miller JS (1997) Mol Cryst Liq Cryst 305:269
Sugiura K-I, Mikami S, Tanaka T, Sawada M, Manson JL, Miller JS, Sakata Y (1997) Chem Lett 1071
Brandon EJ, Arif AM, Miller JS, Sugiura K-I, Burkhart BM (1998) Crystal Eng 1:97
Brandon EJ, Burkhart BM, Rogers RD, Miller JS (1998) Chem Eur J 4:1938
Brandon EJ, Arif AM, Burkhart BM, Miller JS (1998) Inorg Chem 37:2792
Brandon EJ, Rittenberg DK, Arif AM, Miller JS (1998) Inorg Chem 37:3376
Rittenberg DK, Sugiura K-i, Sakata Y, Guzei IA, Rheingold AL, Miller JS (1999) Chem Eur J 5:1874
Rittenberg DK, Sugiura K-I, Sakata Y, Mikami S, Epstein AJ, Miller JS (2000) Adv Mater 12:126
Hibbs W, Rittenberg DK, Sugiura K-I, Burkhart BM, Morin BG, Arif AM, Liable-Sands L, Rheingold AL, Sundaralingam M, Epstein AJ, Miller JS (2001) Inorg Chem 40:1915
Epstein AJ, Wynn CM, Gîrţu MA, Brinckerhoff WB, Sugiura K-i, Miller JS (1997) Molec Cryst Liq Cryst 305:321
Wynn CM, Gîrţu MA, Brinckerhoff WB, Sugiura K-I, Miller JS, Epstein AJ (1997) Chem Mater 9:2156
Wynn CM, Gîrţu MA, Sugiura K-i, Brandon EJ, Manson JL, Miller JS, Epstein AJ (1997) Synth Met 85:1695
Wynn CM, Gîrţu MA, Miller JS, Epstein AJ (1997) Phys Rev B 56:315
Wynn CM, Gîrţu MA, Miller JS, Epstein AJ (1997) Phys Rev B 56:14050
Gîrţu MA, Wynn CM, Sugiura K-I, Miller JS, Epstein AJ (1997) J Appl Phys 81:4410
Gîrţu MA, Wynn CM, Sugiura K-I, Miller JS, Epstein AJ (1997) Synth Metals 85:1703
Lescouezec R, Toma LM, Vaissermann J, Verdaguer M, Delgado FS, Ruiz-Perez C, Lloret F, Julve M (2005) Coord Chem Rev 249:2691
Seiden J (1983) J Phys (Paris) Lett 44:L-947
Brandon EJ, Kollmar C, Miller JS (1998) J Am Chem Soc 120:1822
Ribas-Arino J, Novoa JJ, Miller JS (2006) J Mater Chem 16:2600
Koizumi K, Shoji M, Kitagawa Y, Taniguchi T, Kawakami T, Okumura M, Yamaguchi K (2005) Polyhedron 24:2720
Cimpoesu F, Ferbinteanu M, Frecuş B, Gîrţu MA (2009) Polyhedron 28:2039
Hohenberg P, Kohn W (1964) Phys Rev 136:B864
Kohn W, Sham LJ (1965) Phys Rev A 140:1133
Parr RG, Yang W (1989) Density-functional theory of atoms and molecules. Oxford University Press, New York
Noodleman L, Norman JG (1979) J. Chem Phys 70:4903
Noodleman L (1981) J Chem Phys 74:5737
Bencini A, Totti F (2005) Int J Quant Chem 101:819
Daul CA, Ciofini I, Bencini A (2002) In: Sen KD (ed) Reviews of modern quantum chemistry, part II. World Scientific, Singapore, p 1247
Noodleman L, Peng CY, Case DA, Mouesca JM (1995) Coord Chem Rev 144:199
Nagao H, Nishino M, Shigeta Y, Soda T, Kitagawa Y, Onishi T, Yoshioka Y, Yamaguchi K (2000) Coord Chem Rev 198:265
Ruiz E (2004) Struct Bonding 113:71
Noodleman L, Davidson ER (1986) Chem Phys 109:131
Ruiz E, Alemany P, Alvarez S, Cano J (1997) J Am Chem Soc 119:1297
Ruiz E, Cano J, Alvarez S, Alemany P (1999) J Comput Chem 20:1391
Mitani M, Mori TakanoY, Yamaki D, Yoshioka Y, Yamaguchi K (2000) Chem Phys 113:4035
Onishi T, Takano Y, Kitagawa Y, Kawakami T, Yoshioka Y, Yamaguchi K (2001) Polyhedron 20:1177
Dai D, Whangbo M-H (2003) J Chem Phys 118:29
Shoji M, Koizumi K, Kitagawa Y, Kawakami T, Yamanaka S, Okumura M, Yamaguchi K (2006) ). Chem Phys Lett 432:343
Gorelik EV, Ovcharenko VI, Baumgarten M (2008) Eur J Inorg Chem 2837
Nakanashi Y, Kitagawa Y, Saito T, Kataoka Y, Matsui T, Kawakami K, Okumura M, Yamaguchi K (2009) Int J Quantum Chem 109:3632
Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Montgomery JJA, Vreven T, Kudin KN, Burant JC, Millam JM, Iyengar SS, Tomasi J, Barone V, Mennucci B, Cossi M, Scalmani G, Rega N, Petersson GA, Nakatsuji H, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Klene M, Li X, Knox JE, Hratchian HP, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Ayala PY, Morokuma K, Voth GA, Salvador P, Dannenberg JJ, Zakrzewski VG, Dapprich S, Daniels AD, Strain MC, Farkas O, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Ortiz JV, Cui Q, Baboul AG, Clifford S, Cioslowski J, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Martin RL, Fox DJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A, Challacombe M, Gill PMW, Johnson B, Chen W, Wong MW, Gonzalez C, Pople JA (2004) Gaussian 03, revision C.02. Gaussian, Inc., Wallingford
Becke AD (1998) Phys Rev A 38:3098
Perdew JP (1986) Phys Rev B 33:8822
Rassolov VA, Ratner MA, Pople JA, Redfern PC, Curtiss LA (2001) J Comp Chem 22:976
Becke AD (1988) Phys Rev A 38:3098
Lee C, Yang W, Parr RG (1988) Phys Rev B 37:785
Becke AD (1993) J Chem Phys 98:5648
Bencini A, Totti F (2009) J Chem Theory Comput 5:144
Cabrero J, Calzado CJ, Maynau D, Caballol R, Malrieu JP (2002) J Phys Chem A 106:8146
Acknowledgments
The authors acknowledge financial support from the Romanian Ministry of Education and Research through the CNCSIS-UEFISCSU research grant PN2-Idei-PCCE-239/2010, contract no. 9/2010.
Author information
Authors and Affiliations
Corresponding authors
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Oprea, C.I., Cimpoesu, F., Panait, P. et al. DFT study of structure–properties correlations in [MnTPP][TCNE] quasi-one-dimensional molecular magnets. Theor Chem Acc 129, 847–857 (2011). https://doi.org/10.1007/s00214-011-0943-7
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00214-011-0943-7