While they may have been overshadowed by the brightness of their BODIPY analogues, dipyrrin based metal complexes recently appeared as novel interesting luminescent species owing to development various synthetic strategies for preparation such coordination compounds with appreciable quantum yields and tuneable emission wavelength. Not only rigidification brought functionalization backbone either at position 5 or positions 1 9, but also a careful choice ligands present in complex sphere key...

The use of α,β-unsubstituted dipyrrins, dpm, for the elaboration infinite architectures in crystalline form based on coordination as well hydrogen bonding interactions is reviewed. These ligands can be readily functionalized and derivatives bearing either a peripheral bond donor/acceptor group or secondary coordinating have been developed. In first case, complexes incorporating these dpms self-assemble via leading to extended architectures. second complexes, metallatectons, homonuclear...

The use of deep eutectic solvents (DES) as media for the preparation metal- and covalent organic frameworks (MOFs COFs) their post-synthetic modification towards composites is reviewed.

A series of complexes based on the combination cyclometallated palladium or platinum moieties with functionalized dipyrrin ligands bearing mesityl- benzonitrile groups have been prepared and characterized both in solid state solution; these compounds exhibit a characteristic dipyrrin-centered luminescence an emission intensity modulated by degree rotational freedom aromatic group attached to chelate.

Homo- and hetero-leptic Zn Cu complexes of dipyrrin type ligands bearing mono- di-cyanophenyl groups when combined with silver cations lead to the formation Ag(I)–CC double bond interactions unprecedented in crystalline phase.

Using ligands based on either an acetylacetonate or a dipyrrin moiety appended with pyridyl groups, series of novel heteroleptic copper(II) and cobalt(III) complexes combining both chelate units such as (acacpy2)Cu(dpm-py) (acacpy2)Co(dpm-py)2 (acacpy2 = 1,3-bis(4-pyridyl)-1,3-propanedionate; dpm-py 5-(4-pyridyl)dipyrrin) have been prepared fully characterized. These two were obtained upon reaction the (acacpy2)M homoleptic species (M Cu(II), Co(II)). In solid state, complex behaves...

Sometimes named half-porphyrins, bis-pyrrolic dipyrrin ligands endow their metal complexes with unique properties such as the potential to functionalize heterocyclic backbone or meso position and ability catalyze interesting chemical transformations. Thus, strategies towards derivatization of at group use for formation a broad range polypyrrolic derivatives 2,2'-bis-dipyrrins, nor-/hetero-corroles porphynoids have been elaborated. Furthermore, chelating dipyrrins possibility modifying steric...

The HKUST-1 MOF can not only be synthesized in the green deep eutectic solvent reline (choline chloride/urea 1 : 2) but also converts, upon heating reline, to a 2D non-porous structure incorporating chloride anions.

A recurring secondary building unit is observed in Ca-MOFs prepared deep eutectic solvents based on 1 : 2 combinations of choline chloride and urea derivatives.

Biocompatible cyclodextrin-based metal–organic frameworks (CD-MOFs) form porous suspensions when dispersed in ionic liquids.

(EDT-TTF-CONH2)6[Re6Se8(CN)6], space group R3̄, was prepared by electrocrystallization from the primary amide-functionalized ethylenedithiotetrathiafulvalene, EDT-TTF-CONH2 (E1/21 = 0.49 V vs SCE in CH3CN), and molecular cluster tetraanion, [Re6Se8(CN)6]4- (E1/2 0.33 equipped with hydrogen bond donor acceptor functionalities, respectively. Its Kagome topology is unprecedented for any TTF-based materials. The metallic state observed at room temperature has a strong two-dimensional character,...

The amphoteric 5-(4-cyanophenyl)dipyrrin ligand, offering three distinct states, i.e., cationic, neutral, and anionic, has been exploited for the formation of a 1-D hydrogen-bonded network in its protonated form both homo- heterobinuclear metallamacrocycles, neutral deprotonated respectively, with variety coordination modes.

The use of heteroleptic copper complexes functionalized with two differentiated coordinating groups for the elaboration heterometallic extended networks is presented. Two novel 5-phenyl-dipyrrin (dpm) ligands appended an imidazole or a pyrazole function, dpm-imid and dpm-pz, have been prepared used as synthesis series (acacR)Cu(dpm) (acacH = acetylacetonate; acacCN 3-cyanoacetylacetonate). X-ray crystal structures these revealed that, albeit no particular association mode observed acac...

Abstract Luminescent cyclometalated iridium complexes based on pyridyl appended dipyrrin ligands were prepared and characterized both in the solid state solution. The functionalization of peripheral moiety causes dramatic changes emission properties mono‐ hetero‐ binuclear complexes. A detailed photophysical investigation two mononuclear derivatives [(Ppy) 2 Ir(dpm‐py)] family (Ppy=2‐phenylpyridine, dpm‐py=5‐(4‐pyridyl)dipyrrin) was carried out. Introduction methyl groups at 3 5 positions...

A strategy for the formation of heterometallic coordination polymers based on novel copper(II) and cobalt(III) heteroleptic complexes (acacCN)Cu(dpm) (acacCN)Co(dpm)(2) (acacCN = 3-cyanoacetylacetonate; dpm dipyrrin) is presented. Using dipyrrins appended with a p- or m-pyridyl group, dpm-4py dpm-3py, four copper cobalt were prepared characterized both in solution solid state. These two classes show different electrochemical properties upon investigation by cyclic voltammetry CH(2)Cl(2)....

A series of novel Cd(II) complexes based on α,β-unsubstituted dipyrrin ligands (dpm) has been prepared and characterised both in solution the solid state. These compounds are [Cd(dpm)(2)] type, with coordination sphere metal centre occupied by two dpm chelates. Interestingly, contrast to what reported for Zn(II) analogues, presence a pyridyl- or imidazolyl-appended ligand, number cation can be increased six, leading an octahedral sphere. As consequence, formation 1-, 2-, 3D polymers...

An unprecedented mode of assembly helical motives and Ag(I) ions in the crystalline state is described. The combination a Zn(II) helicate based on 2,2'-bisdpm bearing peripheral benzonitrile moieties with AgX salts, leads to formation tetranuclear core containing Ag-π interactions. Depending coordinating ability X(-) anion solvents used, complex self-assembles into coordination polymers varying dimensionality. From sequence events (Ag-π or Ag-peripheral site), one may envisage two possible...

Both sequential and one-pot strategies for the preparation of a series grid-type mixed metal-organic frameworks (MM'MOFs) based on dipyrrin ligands appended with either pyridyl or phenyl-imidazolyl moiety have been investigated. For stepwise approach, differentiation between two coordination sites (nature, charge, denticity) was exploited synthesis family five discrete Zn(II), Cu(II), Pd(II) complexes. Acting as metallatectons, these construction building blocks lead to formation MM'MOFs...

Luminescent metal–organic frameworks (MOFs) represent interesting materials for applications in detection and sensing, example. While most of these MOFs are based on carboxylate, azole or pyridyl ligands, the dipyrromethene moiety, also referred to as dipyrrin, seems rather appealing. Indeed, this bis-pyrrolic backbone can be readily functionalized act a monoanionic chelate under basic conditions, allowing preparation variety coordination compounds. Some its metal complexes well boron...

Reactions of the unsymmetrical phenol ligand 2-(bis(2-pyridylmethyl)aminomethyl)-6-((2-pyridylmethyl)(benzyl)aminomethyl)-4-methylphenol with Mn(OAc)2·4H2O or Mn(H2O)6(ClO4)2 in presence NaOBz affords dimanganese(II) complexes 1(CH3OH), [Mn2(L)(OAc)2(CH3OH)](ClO4), and 2(H2O), [Mn2(L)(OBz)2(H2O)](ClO4), respectively. On other hand, reaction hydrated manganese(III) acetate furnishes mixed-valent derivative 3(H2O), [Mn2(L)(OAc)2(H2O)](ClO4) 2. The three have been characterized by X-ray...

The first face-capped octahedral clusters with 25 metal-based valence electrons are shown to provide versatile building units capable of engaging in magnetic exchange coupling. Reactions [Re(5)OsSe(8)Cl(6)](3-) and [Re(4)Os(2)Se(8)Cl(6)](2-) NaCN a melt NaNO(3) or KCF(3)SO(3) afford the 24-electron [Re(5)OsSe(8)(CN)(6)](3-) [Re(4)Os(2)Se(8)(CN)(6)](2-). 13C NMR spectrum 13C-labeled version latter species indicates 1:2 mixture cis trans isomers. Cyclic voltammograms acetonitrile display...

The deliberate design of a series single crystals conducting two-dimensional radical cation salts o-bis(amide)-appended ethylenedithiotetrathiafulvalene, β'-[EDT-TTF-(CONH2)2]2X (X = HSO4-, ClO4-, ReO4-, or AsF6-) and their parent monocomponent solid EDT-TTF-(CONH2)2 is demonstrated allows us to reach level prediction the structure molecular conductors. Their conductivity activated with gap 1650 K sizable room-temperature 0.15 S·cm-1 (for X ClO4-) singular spin susceptibility for β'-type...

Reaction of a heteroleptic cyclometalated iridium complex incorporating carboxylic acid appended dipyrrin with copper acetate leads to the formation hexanuclear species paddlewheel structure.

The 5-(benzamide)dipyrrin, a ditopic tecton bearing two different interaction poles, i.e. primary amide as H-bond donor and acceptor deprotonated dipyrrin unit strong chelating group leads in the presence of metal cations (Cu(II), Zn(II..)) or complexes ([Cu(II)-acac]+ [Co(III)-salen]+) to homo- heteroleptic complexes. latter behave metallo-organic tectons generate crystalline phase molecular networks. Whereas homoleptic Cu complex formation 2-D network, its Zn analogue forms 1-D ribbon type...

An imidazole-appended dipyrrin ligand yields, upon coordination to Cu(II) cations, a linear metallatecton that self-assembles with Cd(II) salts afford 2D grid-type MOFs which, parallel stacking, lead porous crystals offering 1D channels.