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035			_a(RuTPU)RU\TPU\network\34625
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090			_a663456
100			_a20210212a2020 k y0engy50 ba
101	0		_aeng
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200	1		_aThe effect of anion complexation on the aromatic properties of aromatic and antiaromatic porphyrinoids† _fR. R. Valiev, L. I. Valiulina, H. Fliegl, D. Sundholm
203			_aText _celectronic
300			_aTitle screen
320			_a[References: 53 tit.]
330			_aThe effect of anion complexation on magnetically induced current densities and excitation energies of antiaromatic molecular rings has been investigated by calculations on expanded antiaromatic porphyrinoids including orangarin, rosarin, amethyrin and on a theoretically predicted strongly antiaromatic hydrocarbon ring. Magnetically induced current densities and the lowest vertical excitation energies have been calculated at the density functional theory (DFT) and time-dependent DFT (TDDFT) levels using the M06-2X functional. Similar calculations have been performed on sapphyrin, cyclo[6]carbon and rubyrin, which are aromatic expanded porphyrinoids. The calculations show that anion complexation weakens the strength of the ring currents and the degree of (anti)aromaticity of the studied porphyrinoids and the antiaromatic hydrocarbon ring, because electronic charge is transferred from the anion to the molecular ring. The anion complexation weakens the calculated ring-current strength susceptibility of the antiaromatic porphyrinoids by 5-7 nA T−1 (25-30%), by 6-16 nA T−1 (21-48%) for the aromatic porphyrinoids, and by 8 nA T−1 (27%) for the antiaromatic hydrocarbon ring, whereas the current-density pathways remain the same for most molecules. Calculations on the lowest excited states show that the electronic excitation transfers electron density from the anion to the molecular ring. An antiaromatic heterocyclic molecular ring with five inner NH moieties that was constructed from the antiaromatic hydrocarbon ring was found to have a large Cl− complexation energy of 67.6 kcal mol−1.
333			_aРежим доступа: по договору с организацией-держателем ресурса
461			_tNew Journal of Chemistry
463			_tVol. 44, iss. 47 _v[P. 20643-20650] _d2020
610	1		_aэлектронный ресурс
610	1		_aтруды учёных ТПУ
701		1	_aValiev _bR. R. _cchemist _cAssistant of Tomsk Polytechnic University _f1983- _gRashid Rinatovich _2stltpush _3(RuTPU)RU\TPU\pers\34114
701		1	_aValiulina _bL. I. _gLenara Ilmirovna
701		1	_aFliegl _bH. _gHeike
701		1	_aSundholm _bD. _gDage
712	0	2	_aНациональный исследовательский Томский политехнический университет _bИсследовательская школа химических и биомедицинских технологий (ИШХБМТ) _c(2017- ) _h8120 _2stltpush _3(RuTPU)RU\TPU\col\23537
801		2	_aRU _b63413507 _c20210212 _gRCR
856	4		_uhttps://doi.org/10.1039/D0NJ04470A
942			_cCF