Site‐selective multi‐emitter gold‐silver metallopolymers: A novel class of self‐assembled materials

Abstract

New luminescent heterometallopolymers [(Au‐C6F5)m(AgOSO2CF3)n (PVP)] with different Au:Ag molar ratios were synthesized. The luminescent emissions of these polymers are strongly dependent on the temperature, excitation wavelengths, and the Au(I):Ag(I) molar ratio. The incorporation of a precise amount of Ag(I) atoms in the backbone of [(Au‐C6F5)m(PVP)] metallopolymer allows a controlled tuning of the emission energy in the green‐blue range.

Investigating the Impact of Packing and Environmental Factors on the Luminescence of Pt(N^N^N) Chromophores

“…A broad emission band between 500 and 600 nm is recorded in all cases that is attributed to 3 MMLCT transition based on previous reports with similar Pt­(N^N^N) compounds. ,,− This means that some kind of aggregation/intermolecular packing should be expected in all cases. An 3 IL contribution is also observed only in the case of 1A with the presence of a vibronic resolution band at higher energies overlapped with the previous one, due to the possibility of several metal environments or different numbers of M···M interactions …”

“…An 3 IL contribution is also observed only in the case of 1A with the presence of a vibronic resolution band at higher energies 51 overlapped with the previous one, due to the possibility of several metal environments or different numbers of M•••M interactions. 20 Additionally, some differences can be observed in the photophysical properties of the triazoles and tetrazoles derivatives. First of all, tetrazole derivatives (compounds 3 and 4A,B) are not emissive in their molecular form but their analogous functionalized polymers are.…”

“…The design and synthesis of coordination polymers, where the metal centers coordinated to specific ligands in a polymeric chain (being the metal part of the polymeric structure), has been extensively explored. − , Nevertheless, the introduction of metallic chromophores as side pending chains within an organic polymer is less explored and even less, the particular use of metal centers suitable to establish metal···metal interactions, playing particular roles in the 2D and 3D structure of metallopolymers or metal coordinating polymers and also in the resulting emissive properties. Regarding this, poly­(4-vinylpyridine), PV, is a very good option due to the presence of pyridyl pending groups, suitable for coordination to a large number of metals and for this reason, it has been used as support of metal-containing polymers, metal nanoparticles, or metal films with several applications such as (photo)­sensing or catalysis. − Nevertheless, the coordination of specific metals well-known to establish metallophilic contacts is scarcely explored. − The use of these metals is of great importance regarding the development of luminescent materials since the resulting photophysical properties are strongly affected by the interplay of different noncovalent interactions such as M···M but also hydrogen bonding, π–π stacking or halogen bonding, among others. − Platinum­(II), with d 8 configuration, is one of the most studied metals suitable for metallophilic contacts and with relevant emissive properties. The involvement of several intra- and intermolecular contacts has resulted in the modulation of the intrinsic luminescence that can be tuned on energies (emission wavelength), intensities (quantum yields), or lifetimes (from a few ns to hundreds of microseconds).…”

Mono‐ and Dinuclear Gold(I) Coumarin Complexes: Luminescence Studies and Singlet Oxygen Production

“…The development of luminescent materials is a research area of great interest in the last decades due to the large variety of applications on different fields such as electronic displays, luminescent switches, OLEDs, optical devices or sensing materials among others. [1][2][3][4][5][6][7][8][9][10] The presence of metal atoms, and particularly, transition metal atoms, in the chemical structure of the designed luminophores is increasing attention due to the intrinsic characteristics that can offer metals regarding enhanced optical properties and chemical configuration with larger variety of coordination numbers that can easily be tuned changing completely the resulting emission with respect to their energy (emission wavelength), intensity (quantum yields) and lifetimes. In particular, heavy atoms are especially relevant on luminescence since they are also very well-known to favor the intersystem crossing (ISC) process from S 1 to T 1 excited states.…”

“…À 1 ): 2975, 2922 ν(C sp3 À H); 1704 ν(C=O); 1596, 1523 (C=C ar ). CDCl 3 ): δ (ppm) = 7.67 (d, J = 9.0 Hz, 1H, 5 CH), 6.61 (dd, J = 9 Hz, J = 3 Hz, 1H,6 CH), 6.49 (d, J = 3 Hz, 1H, 8 CH), 6.13 (s, 1H, 3 CH), 4.47 (m, 6H, CH 2 ), 4.12 (s, 6H, CH 2 ), 4.03 (s, 2H, CH 2 S), 3.42 (q, J = 7 Hz, 4H, N(CH 2 CH 3 ) 2 ), 1.20 (t, J = 7 Hz, 6H, N(CH 2 CH 3 ) 2 ). 31 P{ 1 H} NMR (202 MHz, CDCl 3 ): δ À 49.3 ppm.…”