This communication reports the solvent-free synthesis of a series of copper(I) cyanide (CuCN) -based coordination polymers showing interesting luminescence properties and specific three-dimensional structures. The new compounds have been achieved by directly grinding CuCN together with thiourea (tu), N-methylthiourea (mtu), N-phenylthiourea (ptu), N,N′-diphenylthiourea (dptu), and 2,4-difluorophenylthiourea (fptu). The resulting compounds are [(CuCN)2(tu)]n, [(CuCN)5(mtu)3]n, [(CuCN)3(mtu)2]n, [CuCN(ptu)]n, [CuCN(dptu)]n, and [(CuCN)3(fptu)2]n. “Seeding” crystallization was successful for [(CuCN)2(tu)]n, [CuCN(ptu)]n, [CuCN(dptu)]n, and [(CuCN)3(fptu)2]n, and their structures have been resolved using X-ray single crystal diffraction. Owing to the microcrystalline powdered nature of compounds [(CuCN)5(mtu)3]n and [(CuCN)3(mtu)2]n, their characterization was mainly based on solid-state NMR, via 13C cross polarization magic angle spinning for ligand coordination and 1H magic angle spinning for the weak interactions involving hydrogen atoms. Other solid-state techniques (infrared spectroscopy, X-ray powder diffraction, differential scanning calorimetry, and thermogravimetric analysis) completed the characterization. Finally, the luminescence properties were explored by recording emission and excitation spectra and by evaluating the luminescence quantum yields and lifetimes. Such in-depth study gives promising results for the potential application as luminescent sensors of such compounds.

Solvent-free synthesis of luminescent copper(i) coordination polymers with thiourea derivatives

GRIFASI, FRANCESCA;CHIEROTTI, Michele Remo;GARINO, Claudio;GOBETTO, Roberto;PRIOLA, EMANUELE;DIANA, Eliano;TURCI, Francesco
2015

Abstract

This communication reports the solvent-free synthesis of a series of copper(I) cyanide (CuCN) -based coordination polymers showing interesting luminescence properties and specific three-dimensional structures. The new compounds have been achieved by directly grinding CuCN together with thiourea (tu), N-methylthiourea (mtu), N-phenylthiourea (ptu), N,N′-diphenylthiourea (dptu), and 2,4-difluorophenylthiourea (fptu). The resulting compounds are [(CuCN)2(tu)]n, [(CuCN)5(mtu)3]n, [(CuCN)3(mtu)2]n, [CuCN(ptu)]n, [CuCN(dptu)]n, and [(CuCN)3(fptu)2]n. “Seeding” crystallization was successful for [(CuCN)2(tu)]n, [CuCN(ptu)]n, [CuCN(dptu)]n, and [(CuCN)3(fptu)2]n, and their structures have been resolved using X-ray single crystal diffraction. Owing to the microcrystalline powdered nature of compounds [(CuCN)5(mtu)3]n and [(CuCN)3(mtu)2]n, their characterization was mainly based on solid-state NMR, via 13C cross polarization magic angle spinning for ligand coordination and 1H magic angle spinning for the weak interactions involving hydrogen atoms. Other solid-state techniques (infrared spectroscopy, X-ray powder diffraction, differential scanning calorimetry, and thermogravimetric analysis) completed the characterization. Finally, the luminescence properties were explored by recording emission and excitation spectra and by evaluating the luminescence quantum yields and lifetimes. Such in-depth study gives promising results for the potential application as luminescent sensors of such compounds.
15
6
2929
2939
http://pubs.acs.org/journal/cgdefu
http://pubs.acs.org/doi/abs/10.1021/acs.cgd.5b00352
Chemistry (all); Materials Science (all); Condensed Matter Physics, Thiourea, solid-state NMR, copper, luminescence, quantum yield
Grifasi, Francesca; Chierotti, Michele R.; Garino, Claudio; Gobetto, Roberto; Priola, Emanuele; Diana, Eliano; Turci, Francesco
File in questo prodotto:
File Dimensione Formato  
Thioureas_revised_Final.docx

Accesso riservato

Descrizione: full text
Tipo di file: POSTPRINT (VERSIONE FINALE DELL’AUTORE)
Dimensione 5.08 MB
Formato Microsoft Word XML
5.08 MB Microsoft Word XML   Visualizza/Apri   Richiedi una copia
Thioureas_ESI_revised.docx

Accesso aperto con embargo fino al 30/09/2016

Descrizione: Supporting Information
Tipo di file: MATERIALE NON BIBLIOGRAFICO
Dimensione 1.91 MB
Formato Microsoft Word XML
1.91 MB Microsoft Word XML Visualizza/Apri
cryst growth des2015,15,2929-completo.pdf

Accesso riservato

Descrizione: Articolo completo
Tipo di file: PDF EDITORIALE
Dimensione 5.29 MB
Formato Adobe PDF
5.29 MB Adobe PDF   Visualizza/Apri   Richiedi una copia
Thioureas_revised_Final.pdf

Accesso aperto

Descrizione: preprint
Tipo di file: PREPRINT (PRIMA BOZZA)
Dimensione 1.13 MB
Formato Adobe PDF
1.13 MB Adobe PDF Visualizza/Apri

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/2318/1524034
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 23
  • ???jsp.display-item.citation.isi??? 23
social impact