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Here, we report the facile synthesis of Cu(II) tetraaryl-tetranaphtoporphyrin CuTNP showing an extremely sharp, intense Q band above 700 nm via retro-Diels-Alder approach. The highly saddled structure of CuTNP was confirmed using X-ray single-crystal diffraction. The optical and magnetic properties of CuTNP, as well as its excellent reversible redox behaviours, were thoroughly examined both experimentally and theoretically. The water-soluble nanocomposites encapsulating CuTNP by bent amphiphilic molecules were successfully developed, which kept the intense Q band of CuTNP in water. The strong photoacoustic response of CuTNP was detected, suggesting its potential as a photoacoustic imaging agent. This work provides metal-coordinated linearly π-extended porphyrins as potential functional materials for future biomedical applications. [ABSTRACT FROM AUTHOR]

The rapid appearance of organic optoelectronics as a promising alternative to conventional optoelectronics has been largely achieved through the design and development of new conjugated systems. The 4,4-difluoro-4-bora-3a, 4a-diaza-s-indacene (BODIPY)-based materials have recently emerged as platforms for many types of applications such as sensors, organic thin-film transistors and organic photovoltaics; however, their application as active materials in organic light-emitting diodes (OLEDs) has only been poorly explored. This review article provides an overview of the most important developments in the structural design and synthesis of BODIPY-based organic semiconductors for application in OLED devices. The results summarised and discussed here include the most relevant results starting from the first application of BODIPY-based materials in OLEDs in 2002 up to the recent discoveries as near-IR emitters also promoted by aggregation-induced emission (AIE). Therefore, this review should inspire new research for future developments of BODIPY-based materials, in particular as 'metal-free' infrared emitters. Abbreviations: ACQ: aggregation caused quenching; AIE: aggregation induced emission; Alq3: aluminium tris(8-hydroxyquinoline); BCP: 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline); BDP-PPV: poly(bis(3″,7″-dimethyloctyloxy))p-phenylene vinylene; BF3OEt2: boron trifluoride diethyletherate; BPhen: bathophenanthroline; CBP: 4,40-bis[N-carbazolyl]-2,20-biphenyl; CIE: Commission Internationale de l'Eclairage; DDQ: dichloro-dicyano-quinone; EL: electroluminescence; F8BT: poly(9,9-dioctylfluorene-alt-benzothiadiazole); ITO: indium tin oxide; LEC: light-emitting electrochemical cell; m-MTDATA: 4,4ʹ,4ʹ'-tris[phenyl(m-tolyl)amino]triphenylamine; NPB: N,N′-bis(naphthalen-1-yl)-N,N′-bis(phenyl)benzidine; NPD: N,N'-di(1-naphtyl)-N,N'-diphenylbenzidine; OLED: organic light-emitting diode; OPV: organic photovoltaic; OXD-7: 2,2′-(1,3-phenylene)-bis[5-(4-tert-butylphenyl)-1,3,4-oxadiazole; PBD: 2-(4-biphenylyl)-5(4tert-butyl-phenyl)-1,3,4-oxadiazole; PEDOT: poly(3,4-ethylenedioxythiophene); PLED: polymeric light-emitting diodes; PMMA: polymethylmetacrilate; PPT: 2,8-bis(diphenylphosphoryl)dibenzo[b,d]thiophene; PSS: polystyrene sulphonic sodium salt; PVK: poly(9-N-vinylcarbazole); TPBi: 2,2ʹ,2"-(1,3,5-Benzinetriyl)-tris(1-phenyl-1-H-benzimidazole); TPE: tetraphenylethylene; WOLED: white organic light-emitting diode; 3-TPyMB: tris(2,4,6-trimethyl-3-(pyridin-3-yl)phenyl)borane [ABSTRACT FROM AUTHOR]

Synthesis and properties of a novelmeso-oxo carbaphlorin analogue embedded with anN-free pyrazole moiety are described. TheN-benzyl precursor was prepared by a [3 + 1]-MacDonald condensation ofN-benzyl pyrazole dialdehyde andβ-alkyl-substituted tripyrrane dicarboxylic acid and subsequent oxidation by ferric chloride. Upon deprotection of the benzyl group, the resultingN-free oxophlorin analogue formed a unique supramolecular dimer through mutual hydrogen bonding interactions between the pyrazole NH andmeso-carbonyl group. The assembled behaviour was characterised by various spectroscopies, X-ray crystallographic analysis and vapour pressure osmometry. Under the similar reaction conditions, the condensation ofmeso-phenyl-substituted tripyrrane derivative afforded an unprecedented tetrapyrrolic macrocycle fused with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone unit at theirα-pyrrolic positions. The X-ray crystallographic analysis of the macrocycle revealed a twisted core structure, and nonaromatic nature was elucidated. [ABSTRACT FROM AUTHOR]

Single-crystal X-ray analyses of various 1,3-dipyrrolyl-1,3-propanedione derivatives confirmed the formation of keto-based 1D N-H...O = C hydrogen-bonding chains and cis-enol-based hydrogen-bonding chains. The preferences for keto and enol tautomers in the solid state were found to depend significantly on the positions of substituents at pyrrole rings. α-Aryl-substituted derivatives afford keto forms, while β-alkyl- and β-aryl-substituted derivatives provide cis-enol forms. [ABSTRACT FROM AUTHOR]

We report hierarchical supramolecular organisation promoted by the formation of metallosupramolecular duplex architectures. Three-dimensional supramolecular structure propagation is favoured by long-range aromatic-aromatic interactions towards robust double-helical configuration in 12Zn2+, tubular squared architecture in 22Zn2+ and self-organised triangles in 42Zn2+. The advantageous structural features of such external aromatic interactions are not preserved while introducing new variables such as methylene spacer between imine moiety and the aromatic rings, inducing an orthogonal spatial orientation of the peripheral aromatic arms in 32Zn2+. Indeed, the introduction of supplementary aromatic functionality in 42Zn2+ results in the combination of both internal and external forces and has led to metallosupramolecular triangle architectures that are stabilised by three-dimensional 'diphenylmethane embrace motifs'. The homochiral triangles connected via tetrahedral nodes and face-to-face triangle interactions are organised in the crystal that each duplex constituent has an alternative opposite chirality. [ABSTRACT FROM AUTHOR]

Self-coordination of β-alkyl N-confused porphyrin (NCP) zinc(II) complexes has been studied to reveal that asymmetrical trimers formed exclusively. A key factor to control the configuration of the trimers (symmetric or asymmetric) has been studied theoretically, and revealed that the steric environment around the peripheral nitrogen atoms as well as rotational angles of the confused pyrrole rings play a crucial role in trimer formation of β-alkyl NCP zinc(II) complexes. [ABSTRACT FROM AUTHOR]

Ring closure of 1,2-bis(1-pyrrolylmethyl)benzene in the acid-catalysed condensation with acetone yields the 1,5-diazacyclononatriene [ O -C6H4(CH2NC4H3-2)2C(CH3)2] as the sole identifiable product. The twisted or saddle conformation of the 1,5-diazacyclononatriene, which was confirmed by X-ray crystal structure determination, is conformationally rigid in solution. The conformation of the 1,5-diazacyclononatriene prevents the formation of the target N,N ′-bridged calix[4]pyrrole by further acid-catalysed condensation with acetone, the reaction affording unidentified oligomers/polymers instead. The acid-catalysed condensation of 1,3- and 1,4-bis(1-pyrrolylmethyl)benzene with acetone also yields unidentified oligomers/polymers. [ABSTRACT FROM AUTHOR]