Abstract
This work presents a thorough DFT quantum-chemical characterization of the structural and electronic properties of the benzoquinone–tetrathiafulvalene–benzoquinone (Q–TTF–Q) triad in its neutral and oxidized/reduced states. The minimum-energy structure of the triad in its neutral state corresponds to a C 2v boat conformation, although the planar D 2h structure is also found to be a minimum-energy structure practically degenerate with the boat conformation. Upon oxidation, electrons are mainly extracted from the TTF backbone and the boat-shaped TTF structure evolves toward a planar D 2h and to a twisted D 2 conformation in the cation and dication, respectively. The theoretical characterization of the triad in its radical anion and dianion states is performed with several hybrid (B3LYP, PBE0 and BHHLYP), meta-hybrid (M06-2X) and long-range-corrected (CAM-B3LYP, ωB97X and ωB97XD) functionals. In gas phase, BHHLYP, M06-2X, CAM-B3LYP, ωB97X and ωB97XD functionals correctly predict the localized Q−–TTF–Q structure as the most stable structure, whereas the hybrid B3LYP and PBE0 functionals lead to a delocalized (Q–TTF–Q)− structure. The incorporation of solvent effects is crucial to provide a qualitatively correct description of the anion species where the localized solutions are found to be minimum-energy structures for all the functionals evaluated. The (Q–TTF–Q)2− dianion is predicted to be a biradicaloid species in its electronic ground state. Calculations predict that both Q− → Q0 and TTF → Q0 charge-transfer electronic transitions are associated with the low-energy, broad absorption band experimentally observed for the localized Q−–TTF–Q anion.
Similar content being viewed by others
References
Ferraris J, Walatka V, Perlstei JH, Cowan DO (1973) J Am Chem Soc 95:948–949
Williams JM, Ferraro JR, Thorn RJ, Carlson KD, Geiser U, Wang HH, Kini AM, Whangbo MH (1992) Organic superconductors (including fullerenes). synthesis, structure, properties, and theory. Prentice Hall, Englewoods Cliffs
Organic Conductors: Fundamentals and Applications (1994). Marcel Dekker, New York
Bendikov M, Wudl F, Perepichka DF (2004) Chem Rev 104:4891–4945
Gautier N, Dumur F, Lloveras V, Vidal-Gancedo J, Veciana J, Rovira C, Hudhomme P (2003) Angew Chem Int Ed 42:2765–2768
Dumur F, Gautier N, Gallego-Planas N, Sahin Y, Levillain E, Mercier N, Hudhomme P, Masino M, Girlando A, Lloveras V, Vidal-Gancedo J, Veciana J, Rovira C (2004) J Org Chem 69:2164–2177
Robin MB, Day P (1968) Adv Inorg Chem Radiochem 10:247–422
Heckmann A, Lambert C (2012) Angew Chem Int Ed 51:326–392
Hankache J, Wenger OS (2011) Chem Rev 111:5138–5178
Oton F, Lloveras V, Mas-Torrent M, Vidal-Gancedo J, Veciana J, Rovira C (2011) Angew Chem Int Ed 50:10902–10906
Kaupp M, Renz M, Parthey M, Stolte M, Wurthner F, Lambert C (2011) Phys Chem Chem Phys 13:16973–16986
Cohen AJ, Mori-Sanchez P, Yang WT (2008) Science 321:792–794
Mori-Sánchez P, Cohen AJ, Yang W (2008) Phys Rev Lett 100:146401
Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery JA, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2009) Gaussian 09, Revision A.02 Gaussian, Inc., Wallingford CT
Becke AD (1993) J Chem Phys 98:5648–5652
Lee C, Yang W, Parr RG (1988) Phys Rev B 37:785–789
Francl MM, Pietro WJ, Hehre WJ, Binkley JS, Gordon MS, Defrees DJ, Pople JA (1982) J Chem Phys 77:3654–3665
Perdew JP, Burke K, Ernzerhof M (1996) Phys Rev Lett 77:3865–3868
Adamo C, Barone V (1999) J Chem Phys 110:6158–6170
Zhao Y, Truhlar D (2008) Theor Chem Acc 120:215–241
Yanai T, Tew DP, Handy NC (2004) Chem Phys Lett 393:51
Chai J-D, Head-Gordon M (2008) J Chem Phys 128:084106
Chai J-D, Head-Gordon M (2008) Phys Chem Chem Phys 10:6615–6620
Tomasi J, Mennucci B, Cammi R (2005) Chem Rev 105:2999–3094
Tomasi J, Persico M (1994) Chem Rev 94:2027–2094
Renz M, Theilacker K, Lambert C, Kaupp M (2009) J Am Chem Soc 131:16292–16302
Renz M, Kess M, Diedenhofen M, Klamt A, Kaupp M (2012) J Chem Theory Comput 8:4189–4203
Reed AE, Curtiss LA, Weinhold F (1988) Chem Rev 88:899–926
Jamorski C, Casida ME, Salahub DR (1996) J Chem Phys 104:5134–5147
Petersilka M, Gossmann UJ, Gross EKU (1996) Phys Rev Lett 76:1212–1215
Casida ME, Jamorski C, Casida KC, Salahub DR (1998) J Chem Phys 108:4439–4449
Peach MJG, Benfield P, Helgaker T, Tozer DJ (2008) J Chem Phys 128:044118
Wiggins P, Williams JAG, Tozer DJ (2009) J Chem Phys 131:091101
Jacquemin D, Perpète E, Ciofini I, Adamo C (2011) Theor Chem Acc 128:127–136
Aquilante F, De Vico L, Ferré N, Ghigo G, Malmqvist P-å, Neogrády P, Pedersen TB, Pitoňák M, Reiher M, Roos BO, Serrano-Andrés L, Urban M, Urban M, Veryazov V (2010) J Comput Chem 31:224–247
Ellern A, Bernstein J, Becker JY, Zamir S, Shahal L, Cohen S (1994) Chem Mater 6:1378–1385
Trotter J (1960) Acta Cryst 13:86–95
Hargittai I, Brunvoll J, Kolonits M, Khodorkovsky V (1994) J Mol Struct 317:273–277
Viruela R, Viruela PM, Pou-Amérigo R, Ortí E (1999) Synth Met 103:1991–1992
Wu Q, Voorhis TV (2006) J Chem Phys 125:164105
Vydrov OA, Scuseria GE (2006) J Chem Phys 125:234109
Borden WT, Davidson ER (1977) J Am Chem Soc 99:4587–4594
Borden WT, Iwamura H, Berson JA (1994) Acc Chem Res 27:109–116
Filatov M, Shaik S (1999) J Phys Chem A 103:8885–8889
Autschbach J (2009) Chem Phys Chem 10:1–5
Acknowledgments
This work has been supported by the Spanish Ministry of Economy and Competitiveness (MINECO) (CTQ2009-08790, CTQ2012-31914 and Consolider-Ingenio CSD2007-00010) and the Generalitat Valenciana (PROMETEO/2012/053).
Author information
Authors and Affiliations
Corresponding author
Additional information
Published as part of the special collection of articles derived from the 8th Congress on Electronic Structure: Principles and Applications (ESPA 2012).
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Calbo, J., Aragó, J. & Ortí, E. Theoretical study of the benzoquinone–tetrathiafulvalene–benzoquinone triad in neutral and oxidized/reduced states. Theor Chem Acc 132, 1330 (2013). https://doi.org/10.1007/s00214-013-1330-3
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s00214-013-1330-3