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oai:docta.ucm.es:20.500.14352/185172023-07-18T04:06:46Zcom_20.500.14352_14col_20.500.14352_15

Planarity vs. Non-Planarity in the Electronic Communication of TCAQ-Based Push-Pull Chromophores García, Raúl Calbo, Joaquín Viruela, Rafael Herranz, Maria Ángeles Ortí, Enrique Martín, Nazario 547 Química orgánica (Química) 2306 Química Orgánica Donor-acceptor alkynes, endowed with 11,11,12,12-tetracyano-9,10-anthraquinodimethane (TCAQ) and N,N-dimethylaniline (DMA) units, have been further functionalized by a [2+2] tetracyanoethylene (TCNE) cycloaddition followed by a subsequent retroelectrocyclization to form distorted non-planar molecular structures with 1,1,4,4-tetracyanobuta-1,3-diene (TCBD) bridge ligands. Comprehensive spectroscopic, electrochemical, and computational studies have been carried out to compare the electronic communication in these planar (alkyne) and nonplanar (with TCBD units) TCAQ-based push-pull chromophores. Cyclic voltammetry and UV-Vis absorption measurements confirm a noticeable electronic communication between the TCAQ and DMA units regardless the quasi-orthogonal arrangement of the two dicyanovinyl halves of the TCBD groups, which partially hinder the electronic communication. The experimental trends are strongly supported by theoretical calculations performed at the density functional theory level, which further evidence an active electron-withdrawing role of the TCBD bridge both in the formation of the charged species and in the lowest-lying absorption features. The novel push-pull TCAQ-based derivatives including the TCBD bridge show a broad absorption in the whole visible range while having a structure highly distorted from planarity. These chromophores may therefore be viewed as appealing candidates to be exploited in photovoltaic devices with minimal aggregation phenomena. Unión Europea. FP7 Ministerio de Economía y Competitividad (MINECO) Comunidad de Madrid Unidad de Excelencia María de Maeztu Generalitat Valenciana European Feder Funds Generalitat Valenciana Depto. de Química Orgánica Fac. de Ciencias Químicas TRUE pub 2023-06-17T22:26:58Z 2023-06-17T22:26:58Z 2018 journal article https://hdl.handle.net/20.500.14352/18517 XXXX-XXXX 10.1002/cplu.201700553 eng CHIRALLCARBON (320441) CTQ2014-52045-R, CTQ2015-71154-P, CTQ2016-81911-REDT FOTOCARBON-CM (S2013/MIT-2841) MDM-2015-0538 PROMETEO/2016/135 (CTQ2015- 71154-P) (APOSTD/2017/081) open access application/pdf Wiley Online Library