The versatility of a nitrogen rich pyridinic derivative of the cyclic triimidazole scaffold with C3 symmetry is here exploited to obtain three luminescent coordination polymers (CPs). By reaction of 3,7,11-tri(pyridin-4-yl)triimidazo[1,2-a:1',2'-c:1'',2''-e][1,3,5]triazine, (4py)3TT, with Ag(I), Cd(II) and Cu(I) salts, [Ag{(4-py)3TT}(SO3CF3)]n∙½nCH2Cl2, [Cd{(4-py)3TT}(NO3)2(EtOH)]n and [(Cu2I2)3{(4-py)3TT}4]n·xn(H2O,EtOH) are obtained. The trigonal symmetry of (4py)3TT results in 2D structures with hcb topology in [Ag{(4-py)3TT}(SO3CF3)]n∙½nCH2Cl2 and [Cd{(4-py)3TT}(NO3)2(EtOH)] and a rare 3,4-connected (3,4-c) topology in [(Cu2I2)3{(4-py)3TT}4]n·xn(H2O,EtOH). The multifaceted emissive behaviour of the CPs and the free ligand has been investigated and interpreted through spectroscopic, structural and computational studies. The fluorescence and the high energy phosphorescence of [Ag{(4-py)3TT}(SO3CF3)]n∙½nCH2Cl2, [Cd{(4-py)3TT}(NO3)2(EtOH)]n and (4py)3TT itself are correlated to singlet and triplet excited states of molecular origin while their low energy phosphorescence derives from supramolecular entities associated with strong π-π interactions with little metal contribution as is the case for the single phosphorescence observed for [(Cu2I2)3{(4-py)3TT}4]n·xn(H2O,EtOH). In agreement, unusually long lifetimes in the ms regime are measured for crystals of all compounds.

Layered Ag(I), Cd(II) and Cu(I) Luminescent Coordination Polymers Assembled through a Tri‐pyridyl Cyclic Triimidazole Ligand / D. Malpicci, D. Blasi, A. Forni, E. Lucenti, D. Marinotto, M. Formenti, D. Maver, P. Mercandelli, E. Cariati, L. Carlucci. - In: EUROPEAN JOURNAL OF INORGANIC CHEMISTRY. - ISSN 1434-1948. - 27:21(2024 Jul 22), pp. e202400185.1-e202400185.8. [10.1002/ejic.202400185]

Layered Ag(I), Cd(II) and Cu(I) Luminescent Coordination Polymers Assembled through a Tri‐pyridyl Cyclic Triimidazole Ligand

D. Malpicci
Co-primo
;
D. Blasi
Co-primo
;
A. Forni
Secondo
;
E. Lucenti;D. Marinotto;M. Formenti;D. Maver;P. Mercandelli;E. Cariati
Penultimo
;
L. Carlucci
Ultimo
2024

Abstract

The versatility of a nitrogen rich pyridinic derivative of the cyclic triimidazole scaffold with C3 symmetry is here exploited to obtain three luminescent coordination polymers (CPs). By reaction of 3,7,11-tri(pyridin-4-yl)triimidazo[1,2-a:1',2'-c:1'',2''-e][1,3,5]triazine, (4py)3TT, with Ag(I), Cd(II) and Cu(I) salts, [Ag{(4-py)3TT}(SO3CF3)]n∙½nCH2Cl2, [Cd{(4-py)3TT}(NO3)2(EtOH)]n and [(Cu2I2)3{(4-py)3TT}4]n·xn(H2O,EtOH) are obtained. The trigonal symmetry of (4py)3TT results in 2D structures with hcb topology in [Ag{(4-py)3TT}(SO3CF3)]n∙½nCH2Cl2 and [Cd{(4-py)3TT}(NO3)2(EtOH)] and a rare 3,4-connected (3,4-c) topology in [(Cu2I2)3{(4-py)3TT}4]n·xn(H2O,EtOH). The multifaceted emissive behaviour of the CPs and the free ligand has been investigated and interpreted through spectroscopic, structural and computational studies. The fluorescence and the high energy phosphorescence of [Ag{(4-py)3TT}(SO3CF3)]n∙½nCH2Cl2, [Cd{(4-py)3TT}(NO3)2(EtOH)]n and (4py)3TT itself are correlated to singlet and triplet excited states of molecular origin while their low energy phosphorescence derives from supramolecular entities associated with strong π-π interactions with little metal contribution as is the case for the single phosphorescence observed for [(Cu2I2)3{(4-py)3TT}4]n·xn(H2O,EtOH). In agreement, unusually long lifetimes in the ms regime are measured for crystals of all compounds.
d10 metals; luminescent coordination polymers; nitrogen rich aromatic ligands
Settore CHIM/03 - Chimica Generale e Inorganica
22-lug-2024
24-apr-2024
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/1047488
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