Solid-State Luminescence of Au-Cu-Alkynyl Complexes Induced by Metallophilicity-Driven Aggregation

Igor O. Koshevoy*, Yuh-Chia Chang, Antti J. Karttunen, Julia R. Shakirova, Janne Janis, Matti Haukka, Tapani Pakkanen, Pi-Tai Chou

*Corresponding author for this work

Research output: Contribution to journalArticleScientificpeer-review

Abstract

A new series of homoleptic alkynyl complexes, [{Au2Cu2(C2R)4}n] (R=C3H7O (1), C6H11O (2), C9H19O (3), C13H11O (4)), were obtained from Au(SC4H8)Cl, Cu(NCMe)4PF6, and the corresponding alkyne in the presence of a base (NEt3). Complexes 14 aggregate upon crystallization into polymeric chains through extensive metallophilic interactions. The cluster that contains fluorenolyl functionalities, C13H9O (5), crystallizes in its molecular form as a disolvate, [Au2Cu2(C2C13H9O)4]2THF. The substitution of weakly bound THF molecules with pyridine molecules leads to the complex [Au2Cu2(C2C13H9O)4]2py (6), thus giving two polymorphs in the solid state. Such structural diversity is established through metal-chain and hydrogen-bond formation, which depends on the stereochemical characteristics of the organic ligands. More interestingly, this solid-state structural arrangement affords good emission properties, such as intensity and spectroscopic profile, which are otherwise very weakly emissive in solution. Metallophilic aggregation of the {Au2Cu2} cluster units, as observed in the crystals, results in dramatic enhancement of the room-temperature phosphorescence, thereby reaching a maximum quantum efficiency of 95% (4). A theoretical approach further indicates a synergistic effect of the array of the metal chain upon aggregation, which greatly enhances the spin-orbit coupling and, hence, the phosphorescence, thereby opening up a new direction in the field of aggregate-enhanced emission.

Original languageEnglish
Pages (from-to)5104-5112
Number of pages9
JournalCHEMISTRY: A EUROPEAN JOURNAL
Volume19
Issue number16
DOIs
Publication statusPublished - Apr 2013
MoE publication typeA1 Journal article-refereed

Keywords

  • aggregation
  • copper
  • gold
  • luminescence
  • polymers
  • LIGHT-EMITTING-DIODES
  • CYCLOMETALATED ALKYNYLGOLD(III) COMPLEXES
  • APPROXIMATE COULOMB POTENTIALS
  • DENSITY-FUNCTIONAL METHODS
  • TRIPLET EXCITED-STATES
  • AUXILIARY BASIS-SETS
  • INDUCED EMISSION
  • I COMPLEXES
  • AUROPHILIC INTERACTIONS
  • COPPER(I) COMPLEXES

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