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Download file# Enhanced Diradical Nature in Oxyallyl Derivatives Leads to Near Infra Red Absorption:
A Comparative Study of the Squaraine and Croconate Dyes Using Computational
Techniques^{†}

journal contribution

posted on 2007-05-03, 00:00 authored by Kola Srinivas, Ch. Prabhakar, C. Lavanya Devi, K. Yesudas, K. Bhanuprakash, V. Jayathirtha RaoWe apply many criteria to estimate the diradical character of the ground state singlets of several oxyallyl
derivatives. This is carried out as the oxyallyl derivatives like squaraine and croconate dyes can be represented
by both mesoionic and diradical formulas, the domination of which would characterize its lowest energy
transition. One criterion applied is the singlet−triplet gap, which is known to be inversely proportional to the
diradical character. Another criterion is the occupation number; this is determined for the symmetry broken
state of the molecules in the unrestricted formalism, and the difference of occupation in the HOMO and
LUMO is related to the diradical character. The diradical character of all of the croconates and few squaraines
is estimated to be large. All of these have absorption above 750 nm and can be classified as near infrared
(NIR) dyes, leading to the inference that NIR absorptions in these molecules are largely due to the dominance
of the diradical character. To understand the reliability of the DFT methods for the absorption property
predictions of these molecules, TD−DFT studies to calculate the vertical excitation energies have been carried
out, using the B3LYP/ BLYP exchange correlation functionals and the LB94 asymptotic functional with and
without the inclusion of solvent. The deviations, in both the squaraine series (average lower diradical character),
are found to be systematic, and with the inclusion of the solvent in the calculation, the deviations decrease.
The best least-squares fit with the experimentally observed values using B3LYP /6-311G(d, p) for the symmetric
squaraines yields an

*R*value of 0.92 and, for the unsymmetric squaraines, an*R*value of 0.936. With inclusion of the solvent, the*R*value is 0.96 for the symmetric squaraines and 0.961 for the unsymmetric squaraines, indicating that these DFT functionals with linear scaling may be used to study these systems. The croconate dyes, however, have larger deviation from the experimentally observed values in all of the functionals studied even after inclusion of the solvent effects. The deviations are also not systematic. The deviation with respect to the experiment in this case is attributed to the average larger diradical character in this series.