Rhodium(I)‐centered cyclotriveratrylene

Coolen, H.K.A.C.; Reek, Joost N. H.; Ernsting, Jan Meine; Leeuwen, Piet W. N. M. van; Nolte, Roeland J. M.

doi:10.1002/recl.19951140902

Cited by 3 publications

(3 citation statements)

References 29 publications

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“…The hemicryptophane complex thus obtained is quite flexible, and the cavity is occupied by the spacer arms. 81 The association of two or more CTV units has led to interesting self-assembled supramolecular systems, which present a molecular cavity. We will not report on these cage structures, which are out of the scope of this review.…”

Section: Scheme 14 Synthesis Of Speleands 1 Andmentioning

confidence: 99%

“…The hemicryptophane complex thus obtained is quite flexible, and the cavity is occupied by the spacer arms. 81…”

Section: Chemical Reviewsmentioning

confidence: 99%

“…In 1995 Nolte and co-workers published also a rhodium complex of a CTV ligand bearing three arms terminated by triphenyl phosphite functions. The hemicryptophane complex thus obtained is quite flexible, and the cavity is occupied by the spacer arms …”

Section: Synthesis Of Hemicryptophanesmentioning

confidence: 99%

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Emergence of Hemicryptophanes: From Synthesis to Applications for Recognition, Molecular Machines, and Supramolecular Catalysis

2017

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In the wide area of host-guest chemistry, hemicryptophanes, combining a cyclotribenzylene (or cyclotriveratrylene CTV) unit with another different C-symmetrical moiety, appears as a recent family of molecular cages. The synthesis and recognition properties of the first hemicryptophane were reported in 1982 by Collet and Lehn, but the very little attention received by this class of host compounds in the 20 years following this first promising result can account for their apparent novelty. Indeed, in the last 10 years hemicryptophanes have aroused growing interest, and new aspects have been developed. Thanks to the rigid shaping unit of the north part (CTV) and also the variable and easily functionalized south moiety, hemicryptophanes are revealed to be inherently chiral ditopic host compounds, able to encapsulate various guests, including charged and neutral species. They also enter the field of stimuli-responsive supramolecular systems exhibiting controlled functions. Moreover, endohedral functionalization of their inner cavity leads to supramolecular catalysts. The confinement of the catalytic center affords nanoreactors with improved catalytic activities or selectivities when compared to model systems without a cavity. The current trend shows that reactions in the confined space of synthetic hosts, mimicking enzyme behavior, will expand rapidly in the near future.

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Section: Scheme 14 Synthesis Of Speleands 1 Andmentioning

confidence: 99%

“…The hemicryptophane complex thus obtained is quite flexible, and the cavity is occupied by the spacer arms. 81…”

Section: Chemical Reviewsmentioning

confidence: 99%

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Emergence of Hemicryptophanes: From Synthesis to Applications for Recognition, Molecular Machines, and Supramolecular Catalysis

2017

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Multimetallic and Mixed Environment Iridium(III) Complexes: A Modular Approach to Luminescence Tuning Using a Host Platform

Pritchard

Martir

Zysman‐Colman

et al. 2017

Chemistry A European J

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Mononuclear and trinuclear bis‐cyclometallated IrIII complexes of the host ligands tris(4‐[4′‐methyl‐2,2′‐bipyridyl]methyl)cyclotriguaiacylene (L1) and tris(4‐(4′‐methyl‐2,2′‐ bipyridyl)carboxy)cyclotriguaiacylene (L2) have been prepared. Complexes [{Ir(ppy)2}3(L1)](PF6)3 (1.1), [{Ir(ppy)2}(L1)](PF6)3 (1.2), [{Ir(ppy)2}3(L2)](PF6)3 (2.1) and [{Ir(ppy)2}(L2)](PF6)3 (2.2) (where ppy=phenylpyridinato) showed distinct photophysical properties depending on the L ligand. Complexes featuring the L1 ligand were comparatively blue‐shifted in solution, with longer lifetimes and higher quantum yields. The mixed bis‐cyclometallated IrIII complexes [{Ir(ppy)2}{Ir(dFppy)2}2(L1)](PF6)3 (1.3), [{Ir(ppy)2}{Ir(dFppy)2}2(L2)](PF6)3 (2.3), [{Ir(ppy)2}2{Ir(dFppy)2}(L1)](PF6)3 (1.4) and [{Ir(ppy)2}2{Ir(dFppy)2}(L2)](PF6)3 (2.4) (where dFppy=2,4‐difluorophenylpyrinato) were also synthesised. Steady‐state and time‐resolved spectroscopy, along with electrochemical investigations, show that the Ir(III) chromophores within these mixed Ir‐environment species behave as isolated centres, with no energy transfer or electronic communication between them.

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Playing with podands based on cone-shaped cavities. How can a cavity influence the properties of an appended metal centre?

2005

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The potential of molecules that combine the properties of a conical cavity with those of a covalently-linked transition-metal centre is highlighted through the assessment of cyclodextrin- and calixarene-derived podands ("cavitand" ligands) in coordination chemistry and catalysis. Metallocavitands with coordination sites directed towards the interior of the generic cavity provide interesting systems for studying host-guest complexation processes, their enhanced strength of metal-ion binding allowing for regioselective catalysis in a confined environment, and stabilisation of coordination complexes of unusual forms. Where cavitands have exo-oriented podand arms, the intrinsic dynamics of the cavity can dramatically modify metal chelation behaviour and the catalytic properties of the complexes. Such functionalised cavities are also useful as metal-ion transporters.

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Rhodium(I)‐centered cyclotriveratrylene

Cited by 3 publications

References 29 publications

Emergence of Hemicryptophanes: From Synthesis to Applications for Recognition, Molecular Machines, and Supramolecular Catalysis

Emergence of Hemicryptophanes: From Synthesis to Applications for Recognition, Molecular Machines, and Supramolecular Catalysis

Multimetallic and Mixed Environment Iridium(III) Complexes: A Modular Approach to Luminescence Tuning Using a Host Platform

Playing with podands based on cone-shaped cavities. How can a cavity influence the properties of an appended metal centre?

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