02882nas a2200277   4500008004100000022001400041245010200055210006900157260000800226300001100234490000800245520190900253653001502162653002802177653002202205653003602227653001502263653002302278653004502301100003102346700002102377700002602398700002602424700002502450856012902475       2020                        eng d  a1011-134400aTheoretical study on cyclophane amide molecular receptors and its complexation behavior with TCNQ0 aTheoretical study on cyclophane amide molecular receptors and it  cJAN  a1117350 v2033 a<p>Complexation behavior of cyclophane amide molecular receptors towards 7,7,8,8-tetracyanoquinodimethane (TCNQ) studied. TD-B3LYP/6-31 + G(d,p) based density functional theory was employed to investigate the photophysical characteristics of the complexes obtained. Syn isomers of cyclophane amide molecular hosts show preferred conformation over other conformations. Molecular Orbital analysis indicates the electronic structure change, which reflects in the absorption spectra of the cyclophane amide-1@TCNQ, and cyclophane amide-2@TCNQ charge-transfer (CT) complexes. Binding energy studies with B3LYP-D3/6-31 + G (d,p) theory demonstrated that the more effective binding of the pyridine-2,6-dicarboxamide macrocycles than for their isophthalamide analogs. Both the CT complexes show intermolecular bifurcated hydrogen bonding (N-H-(host)center dot center dot center dot N-(guest)center dot center dot center dot H-N-(host)) interactions (2.06 to 2.08 angstrom), and pi((host))center dot center dot center dot pi((guest)) interactions (3.2 to 3.4 angstrom). Calculated BSSE corrected complexation energy (Delta E) be associated with the formation of the inclusion complexes in the range - 28 to similar to 37 kJ mol(-1), indicating spontaneity of host-guest complex formation in both the cases. From the calculated vibrational spectra of these complexes, the formation of inclusion complexes via N - H-(host)center dot center dot center dot N-(guest) and pi((host))center dot center dot center dot pi((guest)) intermolecular interactions established by the frequency shift in the N - H vibrations. Mulliken population analysis performed to recognize the CT process and the variation in charges between the free and complex TCNQ molecules suggests the intermolecular charge transfer. This study indicates that these cyclophane amides can be a decent CT complexation host for the guests like TCNQ.</p>
10aAbsorption10aCharge transfer complex10aCyclophane amides10aElectrostatic potential surface10aHost-guest10aMolecular orbitals10aTime-dependent density functional theory1 aSundaram, Soma, Sundaram M1 aKarthick, Selvam1 aSailaja, Krishnamurty1 aKarkuzhali, Rajendran1 aGopu, Gopalakrishnan  uhttps://library.ncl.res.in/content/theoretical-study-cyclophane-amide-molecular-receptors-and-its-complexation-behavior-tcnq