Molecular Ruby under Pressure

Angew Chem Int Ed Engl. 2018 Aug 20;57(34):11069-11073. doi: 10.1002/anie.201806755. Epub 2018 Jul 18.

Abstract

The intensely luminescent chromium(III) complexes [Cr(ddpd)2 ]3+ and [Cr(H2 tpda)2 ]3+ show surprising pressure-induced red shifts of up to -15 cm-1 kbar-1 for their sharp spin-flip emission bands (ddpd=N,N'-dimethyl-N,N'-dipyridine-2-yl-pyridine-2,6-diamine; H2 tpda=2,6-bis(2-pyridylamino)pyridine). These shifts surpass that of the established standard, ruby Al2 O3 :Cr3+ , by a factor of 20. Beyond the common application in the crystalline state, the very high quantum yield of [Cr(ddpd)2 ]3+ enables optical pressure sensing in aqueous and methanolic solution. These unique features of the molecular rubies [Cr(ddpd)2 ]3+ and [Cr(H2 tpda)2 ]3+ pave the way for highly sensitive optical pressure determination and unprecedented molecule-based pressure sensing with a single type of emitter.

Keywords: chromium; excited states; luminescence; pressure; spin-flip.