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Fluorescence of New o ‐Carborane Compounds with Different Fluorophores: Can it be Tuned?
Author(s) -
FerrerUgalde Albert,
GonzálezCampo Arántzazu,
Viñas Clara,
RodríguezRomero Jesús,
Santillan Rosa,
Farfán Norberto,
Sillanpää Reijo,
SousaPedrares Antonio,
Núñez Rosario,
Teixidor Francesc
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201402396
Subject(s) - carborane , anthracene , fluorene , chemistry , fluorescence , photochemistry , moiety , phenanthrene , medicinal chemistry , dilithium , fluorophore , diphenyl ether , organic chemistry , deprotonation , ion , physics , quantum mechanics , polymer
Two sets of o ‐carborane derivatives incorporating fluorene and anthracene fragments as fluorophore groups have been successfully synthesized and characterized, and their photophysical properties studied. The first set, comprising fluorene‐containing carboranes 6 – 9 , was prepared by catalyzed hydrosilylation reactions of ethynylfluorene with appropriate carboranylsilanes. The compound 1‐[(9,9‐dioctyl‐fluorene‐2‐yl)ethynyl]carborane ( 11 ) was synthesized by the reaction of 9,9‐dioctyl‐2‐ethynylfluorene and decaborane (B 10 H 14 ). Furthermore, reactions of the lithium salt of 11 with 1 equivalent of 4‐(chloromethyl)styrene or 9‐(chloromethyl)anthracene yielded compounds 12 and 13 . Members of the second set of derivatives, comprising anthracene‐containing carboranes, were synthesized by reactions of monolithium or dilithium salts of 1‐Me‐1,2‐C 2 B 10 H 11 , 1‐Ph‐1,2‐C 2 B 10 H 11 , and 1,2‐C 2 B 10 H 12 with 1 or 2 equivalents of 9‐(chloromethyl)anthracene, respectively, to produce compounds 14 – 16 . In addition, 2 equivalents of the monolithium salts of 1‐Me‐1,2‐C 2 B 10 H 11 (Me‐ o ‐carborane) and 1‐Ph‐1,2‐C 2 B 10 H 11 (Ph‐ o ‐carborane) were reacted with 9,10‐bis(chloromethyl)anthracene to produce compounds 17 and 18 , respectively. Fluorene derivatives 6 – 9 exhibit moderate fluorescence quantum yields (32–44 %), whereas 11 – 13 , in which the fluorophore is bonded to the C cluster (C c ), show very low emission intensity (6 %) or complete fluorescence quenching. The anthracenyl derivatives containing the Me‐ o ‐carborane moiety exhibit notably high fluorescence emissions, with ϕ F =82 and 94 %, whereas their Ph‐ o ‐carborane analogues are not fluorescent at all. For these compounds, we have observed a correlation between the C c C c bond length and the fluorescence intensity in CH 2 Cl 2 solution, comparable to that observed for previously reported styrene‐containing carboranes. Thus, our hypothesis is that for systems of this type the fluorescence may be tuned and even predicted by changing the substituent on the adjacent C c .