Optical Properties of Novel Conjugated Nanohoops: Revealing the Effects of Topology and Size

Abstract

The unique properties of chemical materials are usually related to the topology and size of their constituent unit. Inspired by a previous report on the synthesis of a separable catenane composed of two Mobius-conjugated nanohoops, we theoretically predicted the optical properties of the Mobius monomer, its Huckel analogue, and some structures derived from them. The underlying reasons for the effects of topology and size on molecular (hyper)polarizability and the absorption spectrum were explored from the electronic structure level by means of several analytical methods, including the two-level model, (hyper)polarizability density analysis, and the (hyper)polarizability contribution decomposition. This work is conducive to providing rational design ideas for those who are committed to discovering and synthesizing nanoscale cyclic molecules with special optical properties.

Tuning Electronic Structure and Optical Properties of Li@cyclo[18]carbon Complex via Switching Doping Position of Lithium Atom

“…There is no significant difference between the α iso of Li@C 18 in and Li@C 18 out , which is similar to the law of polarizability between the analogues of many other types of compounds we have studied [41][42][43][44]. However, the change in the way of binding of Li atom not only causes the magnitude of β vec to vary, but also alters the sign of it.…”

“…The (hyper)polarizability density analysis, which graphically exhibits the spatial contribution of electrons in a molecule to electric response properties, is helpful to gain a deep insight into the physical nature of molecular (hyper)polarizability [17,[41][42][43][44]. The (hyper)polarizability densities, namely the local contributions to the respectively, for comparison.…”

Effects of External Field Wavelength and Solvation on the Photophysical Property and Optical Nonlinearity of 1,3-Thiazolium-5-Thiolates Mesoionic Compound

“…Therefore, the field of optical materials has been exploring how to develop new compounds with tunable photophysical properties or enhanced (hyper)polarizabilities for a long time. [4][5][6] So far, researchers have successfully recognized a variety of molecules with exciting optical properties, including inorganic complexes, [7][8][9] organic molecules, [10][11][12][13] metal clusters, 14,15 doped polarizable electrides, 16,17 and even macrocyclic compounds with special topology, 6,18,19 and applied some of them into practice. Among them, the conjugated organic chromophores with electron donating and electron accepting groups at both ends were one of the most popular optical units, partially due to their convenient structural tailoring.…”

Theoretical Framework of 1,3-Thiazolium-5-Thiolates Mesoionic Compounds: Exploring the Nature of Photophysical Properties and Molecular Nonlinearity

“…The analysis of (hyper)polarizability density is helpful in understanding the physical essence of molecular (hyper)polarizability. 25,26,50 The integrand functions of the (hyper)polarizability densities, that is, the local contributions of the (hyper)polarizability, in z direction [ (1) It was observed that except for the distinguishable differences near the electrondonating group, the (1) Displayed in Figure S4 are the local contribution functions of the molecular (hyper)polarizability in x axis of the studied mesoionic compounds under the zerofrequency field. It can be clearly seen that in the isosurface of every order local contributions of the (hyper)polarizability, both the positive and the negative contributions increase with the electron-donating capacity within the molecule.…”