The synthesis as well the structural and photophysical characterization of two isoleptic bis-cyclometalated Pt(II) Pd(II) complexes, namely [PtL] [PdL], bearing a tailored dianionic tetradentate ligand (L2–) are reported. isostructural character intermolecular interactions [PdL] were assessed by NMR spectroscopy X-ray diffraction analysis. Both complexes show fully ligand-controlled aggregation, demonstrating that judicious molecular design can tune properties. In fact, introduction fluorine...

Herein, we describe a photoinitiated and regioselective synthesis of 2-substituted indoles under mild reaction conditions. This biologically privileged scaffold was accessed in good yields from N-aroylbenzotriazoles, quencher class previously identified using our mechanism-based luminescence screening, terminal alkynes the presence photocatalyst blue light irradiation. straightforward protocol displays broad substrate scope functional group tolerance. Furthermore, mildness robustness were...

In this work, we synthesized two tailored phosphorescent Pt(II) complexes bearing a cyclometalating tridentate thiazole-based C^N*N pincer luminophore (L) and exchangeable chlorido ([PtCl(L)]) or cyanido ([PtCN(L)]) coligands. While both showed photoluminescence from metal-perturbed ligand-centered triplet states (3MP-LC), [PtCN(L)] reached the highest phosphorescence quantum yields displayed significant sensitivity toward quenching by 3O2. We encapsulated them into Zn-based metal-organic...

Linking two cyclometalated Pt( ii ) fragments via cyanido bridge improves the luminescence and dramatically enhances aggregation ability resulting in distinct sensitivity to properties of surrounding medium.

Cyclometalated complexes [M(Phbpy)(CN)] (HPhbpy = 6-phenyl-2,2′-bipyridine) of the group 10 metals (Ni, Pd, and Pt) bearing a carbanionic –C∧N∧N pincer ligand were synthesized studied in combined experimental computational DFT approach. All three crystallographically characterized showing closely packed dimers with head-to-tail stacking short metal-metal contacts solid state. The models for geometries, excited states, electronic transitions addressed both monomeric (Ni-mono, Pd-mono,...

In this article, we exploit coordination geometry as a new tool to control the energy landscape and photophysical properties (red <italic>vs.</italic> blue luminescence) of supramolecular polymers.

The three complexes [M(Me2dpb)Cl] (M = Ni, Pd, Pt) containing the tridentate N,C,N-cyclometalating 3,5-dimethyl-1,5-dipyridyl-phenide ligand (Me2dpb−) were synthesised using a base-assisted C‒H activation method. Oxidation potentials from cyclic voltammetry increased along series Pt &lt; Ni Pd 0.15 to 0.74 V. DFT calculations confirmed essentially ligand-centred π*-type character of lowest unoccupied molecular orbital (LUMO) for all in agreement with invariant reduction processes. For...

The synthesis, characterization, and photophysical properties of 16 d8-configured metal complexes featuring Pt(II) or Pd(II) centers with N*N∧C-coordinated ligands is presented. Key findings include the discovery that distortion coordination plane improves solubility, as observed for compounds a pyridine-N-donor instead thiazole unit. In addition, we found substitution chlorido coligand by monodentate cyanido unit enhances emitters' performance decreasing nonradiative decay rate. switch from...

Abstract A series of Pt(II) complexes with tetradentate luminophores has been designed, synthesized, and deposited on coinage metal surfaces the aim to produce highly planar self‐assembled monolayers. Low‐temperature scanning tunneling microscopy (STM) density functional theory (DFT) calculations reveal a significant initial nonplanarity for all complexes. subsequent metal‐catalyzed separation nonplanar moiety at bridging unit via scission C−N bond is observed, leaving behind largely core...

In this work, we explored the synthesis and characterization of Pt(II) complexes bearing different tri- tetradentate luminophores acting as C^N*N- C^N*N^C-chelators. Thus, investigated diverse substitution patterns in order to improve their processability assessed effects structural variations on excited state properties. Hence, a detailed analysis synthetic pathways is presented; photophysical properties were studied by using steady-state time-resolved photoluminescence spectroscopy. We...

Abstract Cyclometalated Pd(II) complexes generally show inferior luminescence properties compared with their Pt(II) analogues. The established approach employing tridentate cyclometalating ligands has allowed us to create a series of square planar [Pd( )X] from protoligands H (2‐(6‐phenylpyridin‐2‐yl)thiazoles and ‐benzothiazoles; coligands X=Cl, Br, I) extensive variations at the C arene group (phenyl, naphthyl, fluorenyl), central N pyridine (pyridine, 4‐phenylpyridine, 3,5‐di‐ tert...

A series of cyclometalated Pt(II) complexes [Pt(C^N^N)X] (X = Cl, CCPh, CCC6F5) was synthesised from the protoligands HC^N^N containing either phenyl (ph), naphthyl (na) or (benzo)thiophenyl (b(th)) C aryl functions and pyridyl (py) (benzo)thiazolyl ((b)tz) peripheral N units, alongside central 4-phenyl-pyridyl (ppy) tBu2-phenyl-pyridyl (tbppy) group. Depending on combination building blocks, these square planar reveal very different electrochemical, UV-vis absorption emission behaviour....

The increase in preorganization associated with coordination geometry changes is exploited to regulate solvation effects and, turn, processability of metallosupramolecular polymers exhibiting close metal–metal contacts.

The electrochemistry and photophysics of the Pt(II) complexes [Pt(naphen)(X)] (Hnaphen = naphtho[1,2-b][1,10]phenanthroline, X Cl or C≡CPh) containing rigid tridentate C^N^N-coordinating pericyclic naphen ligand was studied alongside tetrahydro-derivative [Pt(thnaphen)(X)] (Hthnaphen 5,6,8,9-tetrahydro-naphtho[1,2-b][1,10]phenanthroline) N^C^N-coordinated complex [Pt(bdq)(Cl)] (Hbdq benzo[1,2-h:5,4-h']diquinoline. cyclic voltammetry showed reversible reductions for C^N^N complexes, with...

Abstract Eine Reihe von Pt(II)‐Komplexen mit tetradentaten Luminophoren wurde entworfen, synthetisiert und dem Ziel auf Edelmetalloberflächen aufgebracht, hochplanare selbstassemblierte Monolagen herzustellen. Tieftemperatur‐Rastertunnelmikroskopie (STM) sowie Dichtefunktionaltheorie (DFT)‐Rechnungen zeigen eine erhebliche initiale Nichtplanarität für alle Komplexe. Anschließend metallkatalysierte Spaltung der nichtplanaren Brückeneinheit via C−N Bindungsbruch beobachtet, die einen...

In this study, it is demonstrated that the radiative rate constant of phosphorescent metal complexes can be substantially enhanced using monodentate ancillary ligands containing heavy donor atoms. Thus, chlorido coligand from a Pt(II) complex bearing monoanionic tridentate C^N*N luminophore ([PtLCl]) was replaced by triphenylphosphane (PPh3) and its heavier pnictogen congeners (i.e., PnPh3 to yield [PtL(PnPh3)]). Due high tridentate-ligand-centered character excited states, P-related rather...

In this work, the structural and photophysical characterization of statistical co-crystals based on two homoleptic Pt( ii ) Pd( complexes as well their mechano-responsive properties are reported.

In this study, the insertion of different monodentate co-ligands on Pt(II) complexes bearing a monoanionic C^N*N luminophore as tridentate chelator was achieved beyond previously reported chlorido- ([PtCl(L)]) and cyanido-decorated ([PtCN(L)]) analogues. To investigate impact auxiliary ligand photophysical properties, we introduced neutral carbonyl-ligand observed lower photoluminescence quantum yield (ΦL) than with cyanido moiety. However, direct substitution chlorido co-ligand by...