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Structure and Emissive Properties of Heterobimetallic Ln–Au Coordination Polymers: Role of Tb and Eu in Non-aurophilic [nBu4N]2[Ln(NO3)4Au(CN)2] versus Aurophilic Ln[Au(CN)2]3·3H2O/3D2O Chains

“…Direct excitation of Eu 3+ is differentiated from Au–Eu 3+ energy transfer by the excitation spectra. Eu 3+ can be directly excited at energies of 385, 460, 480, and 495 nm which induce emission peaks around 590 and 690 nm . The expected electric dipole D 0 -F 2 emission of Eu 3+ at 615 nm is not present, yet there are bands associated with Eu 3+ at 590 and 690 nm.…”

“…Eu 3+ can be directly excited at energies of 385, 460, 480, and 495 nm which induce emission peaks around 590 and 690 nm. 38 The expected electric dipole D 0 -F 2 emission of Eu 3+ at 615 nm is not present, yet there are bands associated with Eu 3+ at 590 and 690 nm. This is likely because the symmetry of the Eu is virtually zero so the electric dipole emission is not favored.…”

“…The emissive properties of the 3-D Kagomé-type Ln[Au(CN) 2 ] 3 ·3H 2 O framework, which contains chains of aurophilic interactions throughout the superstructure, has been extensively examined for several different Ln ions. ,− In many cases the use of two emissive elements (Au and Ln) allows for energy transfer between the two in the form of sensitization or quenching. , We also recently reported the use of an analogous non-aurophilic framework: [ n Bu 4 N] 2 [Ln(NO 3 ) 4 Au(CN) 2 ] (Ln = Nd, Eu, Gd, Tb) that does not have inter- or intrachain aurophilic interactions. The lack of efficient energy transfer between the gold and lanthanide in this framework allowed for two distinct chromophores to be observed …”

Ce/Au(CN)2–‐Based Coordination Polymers Containing and Lacking Aurophilic Interactions

“…Indeed, perhaps one of the earliest and most well studied dicyanoaurate‐based coordination polymer systems is the isomorphous set of Ln[Au(CN) 2 ] 3 · 3H 2 O materials, (LnAu 3 , Ln = La,12,13 Pr,14 Nd,15 Sm,16 Eu,17,18 Gd,17,19 Tb,10,20,21 and Dy17) which has a 3‐D network structure replete with aurophilic interactions. This series of materials has been extensively explored with regards to its photoluminescence, wherein the two emissive units, [Au(CN) 2 ] – and Ln III interact in interesting ways such as quenching of one or the other at various temperatures, with accompanying energy transfer and/or sensitization.…”

Heterobimetallic lanthanide–gold coordination polymers: structure and emissive properties of isomorphous [nBu4N]2[Ln(NO3)4Au(CN)2] 1-D chains

“…The previously reported Ln[Au(CN) 2 ] 3 •nH 2 O systems have been well studied in this regard. [11][12][13][14][15][16][17][18][19][20][21][22][23][24] Throughout the Ln[Au(CN) 2 ] 3 •nH 2 O series, various optical phenomena have been observed, including the emission resulting from the efficient energy transfer from [Au(CN) 2 ] − to Ln 3+ , which is ultimately quenched at higher temperatures via a non-radiative charge transfer mechanism in the case of Ln = Eu. In the case of Ln = Tb, the energy transfer from [Au(CN) 2 ] − is not as efficient and Tb 3+ -based emission is quenched at higher temperatures.…”