Near-infrared emitting copper( i ) complexes with a pyrazolylpyrimidine ligand: exploring relaxation pathways

Abstract

Mononuclear copper(I) complexes [CuL2]I (1), [CuL2]2[Cu2I4]·2MeCN (2) and [CuL2]PF6 (3) with a new chelating pyrazolylpyrimidine ligand, 2-(3,5-dimethyl-1H-pyrazol-1-yl)-4,6-diphenylpyrimidine (L), were synthesized. In the structures of complex cations [CuL2]+, Cu+ ions coordinate...

Rhodium(III) Complexes with 2‐(1 H ‐Pyrazol‐1‐yl)pyrimidine Ligands: Synthesis, Structures, Luminescence, and Cytotoxicity

“…All reactants were purchased from commercial suppliers and used as received. The starting rhodium‐containing reagent was rhodium trichloride (Joint Stock Company “The Gulidov Krasnoyarsk Non‐Ferrous Metals Plant”) with a 37.53% rhodium content, 2‐(3,5‐dimethyl‐1 H ‐pyrazol‐1‐yl)‐4,6‐diphenylpyrimidine (HL Me ) [ 78 ] and 2‐(3,5‐diphenyl‐1 H ‐pyrazol‐1‐yl)‐4,6‐diphenylpyrimidine (HL Ph ) [ 79 ] were used as ligands. Single crystals of HL Ph suitable for X‐ray single crystal analysis were obtained by recrystallization from the CH 2 Cl 2 –acetone mixture (1:1).…”

Rhodium(III) Complexes with 2‐(1 H ‐Pyrazol‐1‐yl)pyrimidine Ligands: Synthesis, Structures, Luminescence, and Cytotoxicity

“…All reactants were purchased from commercial suppliers and used as received. The starting rhodium‐containing reagent was rhodium trichloride (Joint Stock Company “The Gulidov Krasnoyarsk Non‐Ferrous Metals Plant”) with a 37.53% rhodium content, 2‐(3,5‐dimethyl‐1 H ‐pyrazol‐1‐yl)‐4,6‐diphenylpyrimidine (HL Me ) [ 78 ] and 2‐(3,5‐diphenyl‐1 H ‐pyrazol‐1‐yl)‐4,6‐diphenylpyrimidine (HL Ph ) [ 79 ] were used as ligands. Single crystals of HL Ph suitable for X‐ray single crystal analysis were obtained by recrystallization from the CH 2 Cl 2 –acetone mixture (1:1).…”

Achieving Deep‐Red TADF with Negative‐Thermal Quenching in [Cu(N^N)(P^P)]⁺ Emitters Through a Perchlorination Strategy

“…Recall that shifting emission into the deep‐red/near‐infrared (NIR) region is highly challenging and examples of such Cu(I) emitters are very rare. [ 19,58–62 ] While targeting NIR emission in [Cu(N^N)(P^P)]⁺ complexes, we found that perchlorinating 1,10‐phenanthroline not only induces a large bathochromic shift but also unexpectedly confers NTQ behavior ( Scheme ). The perchlorination effect also enhances X‐ray luminescence efficiency, highlighting its diverse potential for the design of advanced TADF‐active emitters and scintillators.…”

Interplay of the Cu⋯Cu distance and coordination geometry as a factor affecting the quantum efficiency in dimeric copper( i ) halide complexes with derivatives of 4-pyrazolylpyrimidine-2-thiol

“…80 Previously we have demonstrated that pyrazolylpyrimidines can act as N,N-chelating ligands in the synthesis of emissive copper(I) complexes, including halido complexes with short Cu⋯Cu distances exhibiting bright emission (ESI, Scheme S1 †). [95][96][97][98] In the present study, we synthesized two new pyrazolylpyrimidine ligands, namely 2-benzylthio-4-(3,5dimethyl-1H-pyrazol-1-yl)pyrimidine (L H ) and its methylated analogue 2-benzylthio-4-(3,5-dimethyl-1H-pyrazol-1-yl)-6methylpyrimidine (L Me ) (Scheme 1). Along with the N,N-chelating site, which can be used for binding Cu + ions, these mole-cules contain a sulphur atom which can contribute to populating triplet excited states due to the heavy atom effect.…”

Rhodium(III) Complexes with 2‐(1 H ‐Pyrazol‐1‐yl)pyrimidine Ligands: Synthesis, Structures, Luminescence, and Cytotoxicity

“…All reactants were purchased from commercial suppliers and used as received. The starting rhodium‐containing reagent was rhodium trichloride (Joint Stock Company “The Gulidov Krasnoyarsk Non‐Ferrous Metals Plant”) with a 37.53% rhodium content, 2‐(3,5‐dimethyl‐1 H ‐pyrazol‐1‐yl)‐4,6‐diphenylpyrimidine (HL Me ) [ 78 ] and 2‐(3,5‐diphenyl‐1 H ‐pyrazol‐1‐yl)‐4,6‐diphenylpyrimidine (HL Ph ) [ 79 ] were used as ligands. Single crystals of HL Ph suitable for X‐ray single crystal analysis were obtained by recrystallization from the CH 2 Cl 2 –acetone mixture (1:1).…”

Achieving Deep‐Red TADF with Negative‐Thermal Quenching in [Cu(N^N)(P^P)]⁺ Emitters Through a Perchlorination Strategy

“…Recall that shifting emission into the deep‐red/near‐infrared (NIR) region is highly challenging and examples of such Cu(I) emitters are very rare. [ 19,58–62 ] While targeting NIR emission in [Cu(N^N)(P^P)]⁺ complexes, we found that perchlorinating 1,10‐phenanthroline not only induces a large bathochromic shift but also unexpectedly confers NTQ behavior ( Scheme ). The perchlorination effect also enhances X‐ray luminescence efficiency, highlighting its diverse potential for the design of advanced TADF‐active emitters and scintillators.…”

Interplay of the Cu⋯Cu distance and coordination geometry as a factor affecting the quantum efficiency in dimeric copper( i ) halide complexes with derivatives of 4-pyrazolylpyrimidine-2-thiol

“…80 Previously we have demonstrated that pyrazolylpyrimidines can act as N,N-chelating ligands in the synthesis of emissive copper(I) complexes, including halido complexes with short Cu⋯Cu distances exhibiting bright emission (ESI, Scheme S1 †). [95][96][97][98] In the present study, we synthesized two new pyrazolylpyrimidine ligands, namely 2-benzylthio-4-(3,5dimethyl-1H-pyrazol-1-yl)pyrimidine (L H ) and its methylated analogue 2-benzylthio-4-(3,5-dimethyl-1H-pyrazol-1-yl)-6methylpyrimidine (L Me ) (Scheme 1). Along with the N,N-chelating site, which can be used for binding Cu + ions, these mole-cules contain a sulphur atom which can contribute to populating triplet excited states due to the heavy atom effect.…”

Rhodium(III) Complexes with 2‐(1 H ‐Pyrazol‐1‐yl)pyrimidine Ligands: Synthesis, Structures, Luminescence, and Cytotoxicity

“…All reactants were purchased from commercial suppliers and used as received. The starting rhodium‐containing reagent was rhodium trichloride (Joint Stock Company “The Gulidov Krasnoyarsk Non‐Ferrous Metals Plant”) with a 37.53% rhodium content, 2‐(3,5‐dimethyl‐1 H ‐pyrazol‐1‐yl)‐4,6‐diphenylpyrimidine (HL Me ) [ 78 ] and 2‐(3,5‐diphenyl‐1 H ‐pyrazol‐1‐yl)‐4,6‐diphenylpyrimidine (HL Ph ) [ 79 ] were used as ligands. Single crystals of HL Ph suitable for X‐ray single crystal analysis were obtained by recrystallization from the CH 2 Cl 2 –acetone mixture (1:1).…”

Achieving Deep‐Red TADF with Negative‐Thermal Quenching in [Cu(N^N)(P^P)]⁺ Emitters Through a Perchlorination Strategy

“…Recall that shifting emission into the deep‐red/near‐infrared (NIR) region is highly challenging and examples of such Cu(I) emitters are very rare. [ 19,58–62 ] While targeting NIR emission in [Cu(N^N)(P^P)]⁺ complexes, we found that perchlorinating 1,10‐phenanthroline not only induces a large bathochromic shift but also unexpectedly confers NTQ behavior ( Scheme ). The perchlorination effect also enhances X‐ray luminescence efficiency, highlighting its diverse potential for the design of advanced TADF‐active emitters and scintillators.…”

Interplay of the Cu⋯Cu distance and coordination geometry as a factor affecting the quantum efficiency in dimeric copper( i ) halide complexes with derivatives of 4-pyrazolylpyrimidine-2-thiol

“…80 Previously we have demonstrated that pyrazolylpyrimidines can act as N,N-chelating ligands in the synthesis of emissive copper(I) complexes, including halido complexes with short Cu⋯Cu distances exhibiting bright emission (ESI, Scheme S1 †). [95][96][97][98] In the present study, we synthesized two new pyrazolylpyrimidine ligands, namely 2-benzylthio-4-(3,5dimethyl-1H-pyrazol-1-yl)pyrimidine (L H ) and its methylated analogue 2-benzylthio-4-(3,5-dimethyl-1H-pyrazol-1-yl)-6methylpyrimidine (L Me ) (Scheme 1). Along with the N,N-chelating site, which can be used for binding Cu + ions, these mole-cules contain a sulphur atom which can contribute to populating triplet excited states due to the heavy atom effect.…”