Four new 4,4-difluoro-4-bora-3a,4a-diaza-s-indacen-8-yl (BODIPY) platinum(II) complexes of the type cis-/trans-Pt(BODIPY)Br(PR3)2 (R = Et or Ph) were synthesized and characterized by NMR, electronic absorption, and luminescence spectroscopy. Three of the complexes were also studied by single crystal X-ray diffraction. The absorption profiles of the four complexes feature intense HOMO → LUMO π → π* transitions with molar extinction coefficients ε of ca. 50 000 M(-1)cm(-1) at around 475 nm and vibrational progressions that are characteristic of BODIPYs. Most remarkably, most complexes exhibit dual emissions through fluorescence at ca. 490 nm and phosphorescence at ca. 650 nm that originate from Pt-perturbed BODIPY-centered (1)ππ* or (3)ππ* states, respectively. Electronic absorption and luminescence spectroscopy data are in good agreement with our TD-DFT calculations. While the emission of the cis-complexes is dominated by fluorescence, their trans-isomers emit predominantly through phosphorescence with a phosphorescence quantum yield for trans-Pt(BODIPY)Br(PEt3)2 (trans-1) of 31.2%. trans-1 allows for ratiometric one-component oxygen sensing in fluid solution up to atmospheric concentration levels and exhibits a remarkably high Stern-Volmer constant for the quenching of the excited triplet state by oxygen of ca. 350 bar(-1) as determined by changes in phosphorescence intensity and lifetime.

New square-planar platinum(II) complexes of the type trans-[Pt(PEt3)2(Tx)(X)] (X = Br, Cl, I or CN) bearing a σ-bonded thioxanthon-2-yl (Tx) ligand have been prepared and characterised by X-ray crystallography, cyclic voltammetry, and by NMR and electronic absorption and luminescence spectroscopy. The ligand X hardly influences the electronic transitions, which indicates that the relevant molecular orbitals are largely confined to the Pt-Tx chromophore. In agreement with TD-DFT calculations the energetically lowest electronic transition is assigned as the Tx-centred π→π* HOMO → LUMO excitation. All four complexes display dual emission from the σ-bonded Tx ligand at ca. 450 nm and at ca. 510 nm, which are assigned as fluorescence originating from the (1)π*-state and as phosphorescence originating from the (3)π*-state, respectively. The phosphorescence quantum yield increases with increasing σ-donor strength of the ligand X and reaches a uniquely high value of 18.8% for the chlorido complex Pt-Cl. Switching-on of Tx phosphorescence emission by the Pt(PEt3)2(X) fragment goes along with a reduction of the lifetime of the Tx triplet state from several ms in purely organic derivatives to ca. 2 μs in the complexes.

We report on the platinum complexes trans-Pt(BODIPY)(8-ethynyl-BODIPY)(PEt) (EtBPtB) and trans-Pt(BODIPY)(4-ethynyl-1,8-naphthalimide)(PR) (R = Et, EtNIPtB-1; R = Ph, EtNIPtB-2), which all contain two different dye ligands that are connected to the platinum atom by a direct σ bond. The molecular structures of all complexes were established by X-ray crystallography and show that the different dye ligands are in either a coplanar or an orthogonal arrangement. π-stacking and several CH···F and short CH···π interactions involving protons at the phosphine substituents lead to interesting packing motifs in the crystal. The complexes feature several strong absorptions (ε = 3.2 × 10-5.5 × 10 M cm) that cover the regime from 350 to 480 nm (EtNIPtB-1 and EtNIPtB-2) or from 350 to 580 nm (EtBPtB). Besides the typical absorption bands of both kinds of attached dyes, they also feature an intense band near 400-420 nm, which is assigned by time-dependent density functional theory calculations to a higher-energy transition within the ethynyl-BODIPY (EtB) ligand or to charge transfer between the BODIPY (B) and naphthalimide (NI) chromophores. All complexes show dual fluorescence and phosphorescence emission from either the B (EtNIPtB-1 and EtNIPtB-2) or EtB (EtBPtB) ligand with a maximum phosphorescence quantum yield of 41% for EtNIPtB-1. The latter seems to be the highest reported value for room temperature phosphorescence from a BODIPY dye. The complete quenching of the emission from the chromophore absorbing at the higher energy and the appearance of the corresponding absorption bands in the fluorescence and phosphorescence excitation spectra indicate complete and rapid energy transfer to the chromophore with the lower-energy excited state, i.e., EtNI → B in EtNIPtB-1 and EtNIPtB-2 and B → EtB in EtBPtB. The latter process was further investigated by transient absorption spectroscopy, indicating that energy transfer is complete within 0.6 ns. EtNIPtB-1 catalyzes the photooxidation of 1,5-dihydroxynaphthalene with photogenerated O to Juglone at a much faster rate than methylene blue but with only modest quantum yields of 37% and with the onset of photodegradation after 60 min.

Two pyridine-functionalized coumarins differing with respect to the site of pyridine attachment to the coumarin dye (3 in L1 or 7 in L2) and with respect to the presence (L1) or absence (L2) of a peripheral NMe2 donor were prepared and used as cyclometalating ligands towards the Pt(acac) fragment. X-ray crystal structures of complexes 1 and 2 show strong intermolecular interactions by π-stacking and short Pt•••Pt or C-H•••O hydrogen bonding that result in the formation of sheetlike packing patterns. The NMe2 donor substituent has a profound influence on the absorption and emission properties of the free coumarin dyes; L1 emits strongly while L2 is only weakly emissive. On binding to Pt(acac) the strong fluorescence of L1 is partially quenched while coumarin phosphorescence is observed from cyclometalated L1 and L2. The ligand-centered nature of the LUMO was confirmed by IR spectroelectrochemistry while the assignment of the phosphorescence emission as ligand-based rests on the vibrational structuring, the negligible solvatochromism, the small temperature-induced Stokes shifts on cooling to 77 K, the emission lifetimes, and strong oxygen quenching. (TD-)DFT calculations confirm our experimental results and provide an assignment of the electronic transitions and the spin density distributions in the T1 state. OPEN ACCESS Inorganics 2015, 3 56 Keywords: platinum; emission; coumarin; crystal structure; quantum chemical calculations Chart 1. Structures of complexes 1 and 2. Scheme 1. Synthesis of ligand L2.