Metal-to-ligand charge-transfer sensitisation of near-infrared emitting lanthanides in trimetallic arrays M2Ln (M = Ru, Re or Os; Ln = Nd, Er or Yb)

Pope, Simon J. A. ORCID: https://orcid.org/0000-0001-9110-9711, Coe, Benjamin J., Faulkner, Stephen and Laye, Rebecca H. 2005. Metal-to-ligand charge-transfer sensitisation of near-infrared emitting lanthanides in trimetallic arrays M2Ln (M = Ru, Re or Os; Ln = Nd, Er or Yb). Dalton Transactions 2005 (8) , pp. 1482-1490. 10.1039/b500849b

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Abstract

The new pro-ligand 4-methyl-4′-(carbonylamino(2-(tert-butoxycarbonylamino)ethyl))-2,2′-bipyridyl (L1) has been prepared and used to synthesise the complex fac-ReICl(CO)3(L1) 1 and the complex salts [MII(bipy)2(L1)](PF6)2 (M = RuII8 or OsII15). Deprotection with trifluoroacetic acid affords the amine-functionalised derivatives fac-ReICl(CO)3(L2) 2, [MII(bipy)2(L2)](PF6)2 (M = RuII9 or OsII16) which react with the dianhydride of diethylenetriamine pentaacetic acid (DTPA) to give the binuclear complex {fac-ReICl(CO)3}2(L3) 3 and the complex salts [{MII(bipy)2}2(L3)](PF6)4 (M = RuII10 or OsII17). The latter react with salts Ln(OTf)3 to afford a series of 12 heterotrimetallic compounds that contain a lanthanide (Ln) ion in the DTPA binding site; {fac-ReICl(CO)3}2(L3)LnIII (Ln = Nd 4, Er 5, Yb 6 or Y 7) and [{MII(bipy)2}2(L3)LnIII](PF6)(OTf)3 (M = RuII, Ln = Nd 11, Er 12, Yb 13 or Y 14; M = OsII, Ln = Nd 18, Er 19, Yb 20 or Y 21). All of these trimetallic species display absorption bands ascribed to metal-to-ligand charge-transfer (MLCT) excitations, and luminescence measurements show that these excited states can be used to sensitise near-infrared emission from LnIII (Ln = Nd, Er or Yb) ions. Single crystal X-ray structures of L1 and [RuII(bipy)2(L2H)](H2PO4)3·(CH3)2CO·0.8H2O were obtained, the latter revealing the presence of H2PO4− counter anions, the source of which is presumed to be hydrolysis of PF6− ions.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry
Subjects:	Q Science > QD Chemistry
Publisher:	RSC
ISSN:	1477-9226
Last Modified:	21 Oct 2022 10:53
URI:	https://orca.cardiff.ac.uk/id/eprint/41637

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