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Diradical character of neutral heteroleptic bis(1,2-dithiolene) metal complexes : case study of [Pd(Me2timdt)(mnt)] (Me2timdt = 1,3-dimethyl-2,4,5-trithioxoimidazolidine; mnt2– = 1,2-dicyano-1,2-ethylenedithiolate)
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dc.contributor.author | Aragoni, M. Carla | |
dc.contributor.author | Caltagirone, Claudia | |
dc.contributor.author | Lippolis, Vito | |
dc.contributor.author | Podda, Enrico | |
dc.contributor.author | Slawin, Alexandra Martha Zoya | |
dc.contributor.author | Woollins, J Derek | |
dc.contributor.author | Pintus, Anna | |
dc.contributor.author | Arca, Massimiliano | |
dc.date.accessioned | 2021-11-13T00:45:10Z | |
dc.date.available | 2021-11-13T00:45:10Z | |
dc.date.issued | 2020-11-13 | |
dc.identifier | 270914887 | |
dc.identifier | 5f913f1a-0b4f-47a9-9357-c5573344f54e | |
dc.identifier | 85096627198 | |
dc.identifier | 000599190300069 | |
dc.identifier.citation | Aragoni , M C , Caltagirone , C , Lippolis , V , Podda , E , Slawin , A M Z , Woollins , J D , Pintus , A & Arca , M 2020 , ' Diradical character of neutral heteroleptic bis(1,2-dithiolene) metal complexes : case study of [Pd(Me 2 timdt)(mnt)] (Me 2 timdt = 1,3-dimethyl-2,4,5-trithioxoimidazolidine; mnt 2– = 1,2-dicyano-1,2-ethylenedithiolate) ' , Inorganic Chemistry , vol. Articles ASAP . https://doi.org/10.1021/acs.inorgchem.0c02696 | en |
dc.identifier.issn | 0020-1669 | |
dc.identifier.other | ORCID: /0000-0002-9527-6418/work/83889423 | |
dc.identifier.other | ORCID: /0000-0002-1498-9652/work/83889434 | |
dc.identifier.uri | https://hdl.handle.net/10023/24331 | |
dc.description | M. A., M. C. A., C. C., and V. L. thank the Fondazione di Sardegna (FdS) and Regione Autonoma della Sardegna (RAS) (Progetti Biennali di Ateneo FdS/RAS annualità 2018) for financial support. A.P. acknowledges RAS for the funding in the context of the POR FSE 2014−2020 (CUP F24J17000190009). | en |
dc.description.abstract | The reaction of the bis(1,2-ditiolene) complex [Pd(Me2timdt)2] ( 1 ; Me2timdt•– = monoreduced 1,3-dimethyl-2,4,5-trithioxoimidazolidine) with Br2 yielded the complex [Pd(Me2timdt)Br2] ( 2 ), which was reacted with Na2mnt (mnt2– = 1,2-dicyano-1,2-ethylenedithiolate) to give the neutral mixed-ligand complex [Pd(Me2timdt)(mnt)] ( 3 ). Complex 3 shows an intense solvatochromic near-infrared (NIR) absorption band falling between 955 nm in DMF and 1060 nm in CHCl3 (ε = 10700 M–1 cm–1 in CHCl3). DFT calculations were used to elucidate the electronic structure of complex 3 , and to compare it with those of the corresponding homoleptic complexes 1 and [Pd(mnt)2] ( 4 ). An in-depth comparison of calculated and experimental structural and vis–NIR spectroscopic properties, supported by IEF-PCM TDDFT and NBO calculations, clearly points to a description of 3 as a dithione-dithiolato complex. For the first time, a Broken-Symmetry (BS) procedure for the evaluation of the singlet diradical character (DC) of heteroleptic bis(1,2-dithiolene) complexes has been developed and applied to complex 3 . The DC, predominant for 1 (nDC = 55.4%), provides a remarkable contribution to the electronic structures of the ground states of both 3 and 4, showing a diradicaloid nature (nDC = 24.9% and 27.5%, respectively). The computational approach developed here clearly shows that a rational design of the DC of bis(1,2-ditiolene) metal complexes, and hence their linear and nonlinear optical properties, can be achieved by a proper choice of the 1,2-dithiolene ligands based on their electronic structure. | |
dc.format.extent | 3515302 | |
dc.language.iso | eng | |
dc.relation.ispartof | Inorganic Chemistry | en |
dc.subject | 1,2-dithiolene | en |
dc.subject | Palladium | en |
dc.subject | DFT | en |
dc.subject | Push-pull | en |
dc.subject | Broken symmetry | en |
dc.subject | NLO | en |
dc.subject | QD Chemistry | en |
dc.subject | DAS | en |
dc.subject.lcc | QD | en |
dc.title | Diradical character of neutral heteroleptic bis(1,2-dithiolene) metal complexes : case study of [Pd(Me2timdt)(mnt)] (Me2timdt = 1,3-dimethyl-2,4,5-trithioxoimidazolidine; mnt2– = 1,2-dicyano-1,2-ethylenedithiolate) | en |
dc.type | Journal article | en |
dc.contributor.institution | University of St Andrews. School of Chemistry | en |
dc.contributor.institution | University of St Andrews. EaSTCHEM | en |
dc.identifier.doi | 10.1021/acs.inorgchem.0c02696 | |
dc.description.status | Peer reviewed | en |
dc.date.embargoedUntil | 2021-11-13 |
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