A luminescent 1D silver polymer containing [2.2]paracyclophane ligands

Funding: UK EPSRC Grant Number(s) EP/P014082/1, EP/M02105X/1, EP/R035164/1).[2.2]Paracyclophane scaffolds have seen limited use as building blocks in supramolecular chemistry. Here, we report the synthesis and characterization of a 1D coordination polymer consisting of silver(I) ions bound to a [2.2]paracyclophane scaffold functionalized with two 4-pyridyl units. The structure of the polymer has been determined from single crystal X-ray diffraction analysis and reveals two different silver coordination motifs that alternate along the 1D coordination polymer. The coordination polymer exhibits strong blue and sky-blue fluorescence in solution and in the crystalline solid state, respectively.Publisher PDFPeer reviewe

Exploring the self-assembly and energy transfer of dynamic supramolecular iridium-porphyrin systems

EZ-C acknowledges the University of St Andrews for financial support. IDWS acknowledges support from EPSRC (EP/J009016) and the European Research Council (grant 321305). IDWS also acknowledges support from a Royal Society Wolfson research merit award. DJ acknowledges the European Research Council (grant: 278845) and the RFI Lumomat for financial support.We present the first examples of dynamic supramolecular systems composed of cyclometalated Ir(III) complexes of the form of [Ir(C^N)2(N^N)]PF6 (where C^N is mesppy = 2-phenyl-4-mesitylpyridinato and dFmesppy = 2-(4,6-difluorophenyl)-4-mesitylpyridinato and N^N is 4,4':2',2'':4'',4'''-quaterpyridine, qpy) and zinc tetraphenylporphyrin (ZnTPP), assembled through non-covalent interactions between the distal pyridine moieties of the qpy ligand located on the iridium complex and the zinc of the ZnTPP. The assemblies have been comprehensively characterized by a series of analytical techniques (1H NMR titration experiments, 2D COSY and HETCOR NMR spectra and low temperature 1H NMR spectroscopy) and the crystal structures have been elucidated by X-ray diffraction. The optoelectronic properties of the assemblies and the electronic interaction between the iridium and porphyrin chromophoric units have been explored with detailed photophysical measurements, supported by time-dependent density functional theory (TD-DFT) calculations.PostprintPeer reviewe

Linearer und nichtlinearer Ladungstraegertransport in Naphtalin-Kristallen

With 115 refs.SIGLECopy held by FIZ Karlsruhe; available from UB/TIB Hannover / FIZ - Fachinformationszzentrum Karlsruhe / TIB - Technische InformationsbibliothekDEGerman

Biodegradable hollow silica nanospheres containing gold nanoparticle arrays

We introduce biodegradable hollow silica nanocapsules embedding arrays of 3 nm gold nanoparticles. The silica shell degrades in full serum in a few hours, potentially allowing the clearance of the capsules and their contents by the efficient renal pathway, and thereby overcoming accumulation issues typical of metal nanoparticles

Biodegradable nano-architectures containing gold nanoparticles arrays

One of the major concerns regarding the clinical translation of metal nanoparticles is related to the question of their persistence in organisms that can increase the likelihood of toxicity and the interaction/interference with common medical diagnoses. In order to overcome these issues we have recently introduced a versatile 90 nm nano-architecture composed by: i) arrays of 3 nm gold nanoparticles, ii) functionalizable commercial polymers surrounding the gold nanoparticles, and iii) biodegradable and derivatizable silica shell embedding the polymer-nanoparticle assembly. These robust nanocapsules maintain the intriguing features of gold nanospheres but are biodegraded in physiological media to their potentially renal clearable building blocks

A luminescent [Pd₄Ru₈]²⁴⁺ supramolecular cage

A phosphorescent cage of the form [Pd₄Ru₈]²⁴⁺ is reported. The cage was formed using the metalloligand [Ru(dtbubpy)₂(qpy)]²⁺, where qpy = 4,4′:2′,2′′:4′′,4′′′-quaterpyridine and dtbubpy = 4,4′-di-tert-butyl-2,2′-bipyridine. The cage has been characterised by NMR, ESI-MS, TEM and X-ray diffraction analyses and its emission properties elucidated by steady-state and time-resolved emission spectroscopy

Structure-switching M₃L₂ Ir(III) coordination cages with photo-isomerising azo-aromatic linkers

Cyclotriguaiacylene has been functionalised with 3- or 4-pyridyl-azo-phenyl groups to form a series of molecular hosts with three azobenzene-type groups that exhibit reversible photo-isomerisation. Reaction of the host molecules with [Ir(C^N)₂(NCMe)₂]+ where C^N is the cyclometallating 2-phenylpyridinato, 2-(4-methylphenyl)pyridinato or 2-(4,5,6-trifluorophenyl)pyridinato results in the self-assembly of a family of five different [{Ir(C^N)₂}₃(L)₂]³+ coordination cages. Photo-irradiation of each of the cages with a high energy laser results in E → Z photo-isomerisation of the pyridyl-azo-phenyl groups with up to 40% of groups isomerising. Isomerisation can be reversed by exposure to blue light. Thus, the cages show reversible structure-switching while maintaining their compositional integrity. This represents the largest photo-induced structural change yet reported for a structurally-integral component of a coordination cage. Energy minimised molecular models indicate a switched cage has a smaller internal space than the initial all-E isomer. The [Ir(C^N)₂(NCMe)₂]+ cages are weakly emissive, each with a deep blue luminescence at ca. 450 nm

Exploring the self-assembly and energy transfer of dynamic supramolecular iridium-porphyrin systems

We present the first examples of dynamic supramolecular systems composed of cyclometalated Ir(III) complexes of the form of [Ir(C^N)2(N^N)]PF6 (where C^N is mesppy = 2-phenyl-4-mesitylpyridinato and dFmesppy = 2-(4,6-difluorophenyl)-4-mesitylpyridinato and N^N is 4,4':2',2'':4'',4'''-quaterpyridine, qpy) and zinc tetraphenylporphyrin (ZnTPP), assembled through non-covalent interactions between the distal pyridine moieties of the qpy ligand located on the iridium complex and the zinc of the ZnTPP. The assemblies have been comprehensively characterized by a series of analytical techniques (1H NMR titration experiments, 2D COSY and HETCOR NMR spectra and low temperature 1H NMR spectroscopy) and the crystal structures have been elucidated by X-ray diffraction. The optoelectronic properties of the assemblies and the electronic interaction between the iridium and porphyrin chromophoric units have been explored with detailed photophysical measurements, supported by time-dependent density functional theory (TD-DFT) calculations