Document Detail

Luminescent gold-silver complexes derived from neutral bis(perfluoroaryl)diphosphine gold(i) precursors.
MedLine Citation:
PMID:  23340740     Owner:  NLM     Status:  Publisher    
Complex [Au{4-C(6)F(4)(4-C(6)BrF(4))}(tht)] reacts with diphosphines (L-L) such as bis(diphenylphosphino)methane (dppm) or 1,2-bis(diphenylphosphino)benzene (dppb) in a 2 : 1 molar ratio in dichloromethane, leading to neutral products of stoichiometry [(Au{4-C(6)F(4)(4-C(6)BrF(4))})(2)(μ-L-L)] (L-L = dppm (), dppb ()). In the crystal structure of complex short AuAu interactions of 2.9367(5) and 2.9521(5) Å appear. This complex displays an orange emission, which is assigned to arise from a charge transfer transition from a metal centered Au-Au orbital to an orbital located at the diphosphine ligand. Addition of silver trifluoroacetate to these complexes in a 1 : 1 or a 2 : 1 molar ratio generates polymeric heterometallic gold-silver compounds of stoichiometry [Ag(2)Au(2){4-C(6)F(4)(4-C(6)BrF(4))}(2)(CF(3)CO(2))(2)(μ-L-L)](n) (L-L = dppm (), dppb ()), which confirms the capability of the neutral [(Au{4-C(6)F(4)(4-C(6)BrF(4))})(2)(μ-diphosphine)] units to act as electron density donors when treated with a Lewis acid substrate. These heterometallic derivatives show blue emissions indicating large HOMO-LUMO band gaps, due to the stabilization that the gold-based HOMO orbitals suffer when the electron withdrawing silver trifluoroacetate fragments interact with them.
R Vilma Bojan; Rafal Czerwieniec; Antonio Laguna; Tania Lasanta; José M López-de-Luzuriaga; Miguel Monge; M Elena Olmos; Harmut Yersin
Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2013-1-23
Journal Detail:
Title:  Dalton transactions (Cambridge, England : 2003)     Volume:  -     ISSN:  1477-9234     ISO Abbreviation:  Dalton Trans     Publication Date:  2013 Jan 
Date Detail:
Created Date:  2013-1-23     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  101176026     Medline TA:  Dalton Trans     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
Departamento de Química, Universidad de La Rioja, Centro de Investigación en Síntesis Química (CISQ), Complejo Científico-Tecnológico, 26004-Logroño, Spain.
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