title: Polynuclear cage-like Au(i) phosphane complexes based on a S2-template: observation of multiple luminescence in coordinated polyaromatic systems.
abstract: A rational approach to the synthesis of cage-like compounds has been realized to build a new family of sulfido-phosphane Au(i) polynuclear complexes. Ditopic phosphane ligands with an extended aromatic system were used to obtain cage compounds with a clearly determined geometry. Au(i) complexes have been fully characterised in solution using spectroscopy methods, and DFT optimisation of the molecular structure gives additional arguments in favour of the suggested structural patterns. All complexes obtained are luminescent in solution and in the solid state, and display multiple emissions with an unusual combination of two phosphorescence bands and one fluorescence band. DFT calculations show that multiple emissions were mainly determined by1IL and metal perturbed3IL transitions. The ratio of singlet and triplet emission components depends on the distance between the ligand chromophoric centre and Au(i).
authors.affiliation: St. Petersburg State University, Institute of Chemistry, Universitetskii pr. 26, 198504 St. Petersburg, Russia. stunik@inbox.ru.
authors.forename: Julia R
authors.identifier: http://orcid.org/0000-0001-8342-4893
authors.initials: JR
authors.lastname: Shakirova
authors.affiliation: St. Petersburg State University, Institute of Chemistry, Universitetskii pr. 26, 198504 St. Petersburg, Russia. stunik@inbox.ru.
authors.forename: Elena V
authors.identifier: http://orcid.org/0000-0003-4046-7708
authors.initials: EV
authors.lastname: Grachova
authors.affiliation: St. Petersburg State University, Institute of Chemistry, Universitetskii pr. 26, 198504 St. Petersburg, Russia. stunik@inbox.ru.
authors.forename: Vladimir V
authors.identifier: http://orcid.org/0000-0001-7200-1561
authors.initials: VV
authors.lastname: Sizov
authors.affiliation: St. Petersburg State University, Institute of Chemistry, Universitetskii pr. 26, 198504 St. Petersburg, Russia. stunik@inbox.ru.
authors.forename: Galina L
authors.identifier: http://orcid.org/0000-0003-1153-3999
authors.initials: GL
authors.lastname: Starova
authors.affiliation: University of Eastern Finland, 80101 Joensuu, Finland.
authors.forename: Igor O
authors.initials: IO
authors.lastname: Koshevoy
authors.affiliation: St. Petersburg State University, Department of Physics, 198504 St. Petersburg, Russia and Institute of Nanobiotechnologies, Peter the Great St. Petersburg Polytechnic University, 195251 St. Petersburg, Russia.
authors.forename: Alexey S
authors.initials: AS
authors.lastname: Melnikov
authors.affiliation: Universidad de Zaragoza-CSIC, Departamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), 50009 Zaragoza, Spain.
authors.forename: M Concepción
authors.initials: MC
authors.lastname: Gimeno
authors.affiliation: Universidad de Zaragoza-CSIC, Departamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), 50009 Zaragoza, Spain.
authors.forename: Antonio
authors.initials: A
authors.lastname: Laguna
authors.affiliation: St. Petersburg State University, Institute of Chemistry, Universitetskii pr. 26, 198504 St. Petersburg, Russia. stunik@inbox.ru.
authors.forename: Sergey P
authors.identifier: http://orcid.org/0000-0002-9431-0944
authors.initials: SP
authors.lastname: Tunik