Taking advantage of the outstanding oxygen-sensitive luminescence properties of the previously synthesised Tb(III) complex [{(MeMeArO)3tacn}LnIII(THF)] (1Tb, Ln = Tb), herein, we have prepared an oxygen sensor based on 1Tb embedded in polystyrene film (1Tb/PS) and found that 1Tb/PS shows the highest sensitivity (I0/I100 = 14.9) and the fastest response (response/recovery time = 1.9 s/2.9 s), among the lanthanide(III)-based oxygen sensors with f–f emission. Moreover, we have prepared the lanthanide(III)-based colorimetric luminescent oxygen sensor (1TbSm/PS) with green–yellow–red responses, by using 1Tb and a newly synthesised oxygen-insensitive Sm(III) complex (1Sm, Ln = Sm; Φ = 0.010 and τ = 12.2 μs).

Rod-like millimetre-size crystals of a newly prepared rhodium dithionite complex with n-pentyl moieties bend upon photoirradiation and return to the initial shape upon heating; the roles of the flexible n-pentyl moieties as well as the photoreactive dithionite unit (μ-O2SSO2) are disclosed by single crystal X-ray diffraction.

Coordination environment of the Tb3+ ion in oxygen-sensitive luminescent complexes can be successfully controlled through the size of alkyl substituents on ligands {(RMeArOH)4cyclen} (R = tBu or Me; cyclen = 1,4,7,10-tetraazacyclododecane); a newly prepared eight-coordinate complex 1tBu shows higher oxygen sensitivity (KSV = 17 600) and lower luminescence quantum yield (Φ = 0.67 under N2) than those of the previously reported seven-coordinate analogues 1Me and [{(MeMeArO)3tacn}TbIII(THF)] (KSV = 12 600 and 8300, Φ = 0.91 and 0.91 under N2, respectively; tacn = 1,4,7-triazacyclononane; THF = tetrahydrofuran). The oxygen-sensitive mechanism is discussed on the basis of the photophysical properties of the corresponding Gd(III) complexes.

This paper presents a gadolinium(III) complex that shows blue phosphorescence in the crystalline state at room temperature under air atmosphere; color of the crystals can be changed to pale-green from blue by doping of 1-naphthol.

This paper presents the first dysprosium(III) complex, [{(MeMeArO)3tacn}DyIII(THF)] (1Dy), that shows oxygen-sensitive luminescence. The synthesis, structure and oxygen-sensitive luminescence properties of 1Dy are reported (Φ = 0.050 and τ = 17.7 μs under N2, Φ = 0.011 and τ = 4.1 μs under O2 and KSV = 305 M−1 in THF; KSV = 0.0077%−1 in polystyrene film). The oxygen sensitive mechanism of 1Dy is discussed based on the photophysical properties of the corresponding gadolinium(III) complex, [{(MeMeArO)3tacn}GdIII(THF)].

This paper presents a 1,4,7,10-teraazacyclododecane-based tetrakis-phenol as a protonated ligand precursor and its oxygen-sensitive luminescent terbium(III) complex with an extendable phenol pendant arm (Φ = 0.91 under N2, Φ = 0.031 under air), in which the potentially N4O4-octadentate ligand unprecedentedly coordinates to the Tb3+ ion in a N4O3-heptadentate fashion.

This communication presents a new terbium(III) complex that shows the highest luminescence quantum yield among the oxygen-sensitive lanthanide complexes (Φ = 0.91 under N2, Φ = 0.054 under air).

A new class of efficient catalyst, the Rh(I) complex [(η5-C5Me5)RhI(bpy)] (1; bpy = 2,2′-bipyridine), for the C–F bond hydrogenolysis of fluoroaromatics (C6F5CF3, C6F6, C6F5H, and C6F5CH3) is presented. The best turnover number of 380 for C6F6 is afforded by using 0.1 mol % of 1, 0.8 MPa of H2, and 2 equiv of Et2NH in CH3CN at 25 °C. The successful isolation of the C–F bond cleavage product [(η5-C5Me5)RhIII(bpy)(C6F5)](F) as a plausible intermediate of the catalytic hydrogenolysis of C6F6 by 1 is also described.

A naphthyl-substituted pentamethylcyclopentadienyl ligand (CpNaph = η5-C5Me4CH2C10H7) and its Sm(II) complexes [Sm(CpNaph)2(THF)x] (1: x = 2, 2: x = 0) have been prepared and characterised. The solvent-induced reversible conversion between the di-THF solvated purple complex 1 and the un-solvated dark green complex 2 is presented.

A photoreactive rhodium dithionite complex [(RhCpEt)2(μ-CH2)2(μ-O2SSO2)] (1Et) with CpEt (η5-C5Me4Et) ligands was newly synthesized. Upon short-time irradiation with low intensity light, two kinds of stepwise surface morphology changes of the crystal 1Et were observed. Prolonged irradiation with high intensity light caused cracking and breaking down of the crystal.

This paper presents a gadolinium(III) complex that shows blue phosphorescence in the crystalline state at room temperature under air atmosphere; color of the crystals can be changed to pale-green from blue by doping of 1-naphthol.

A photoreactive rhodium dithionite complex [(RhCpEt)2(μ-CH2)2(μ-O2SSO2)] (1Et) with CpEt (η5-C5Me4Et) ligands was newly synthesized. Upon short-time irradiation with low intensity light, two kinds of stepwise surface morphology changes of the crystal 1Et were observed. Prolonged irradiation with high intensity light caused cracking and breaking down of the crystal.

A naphthyl-substituted pentamethylcyclopentadienyl ligand (CpNaph = η5-C5Me4CH2C10H7) and its Sm(II) complexes [Sm(CpNaph)2(THF)x] (1: x = 2, 2: x = 0) have been prepared and characterised. The solvent-induced reversible conversion between the di-THF solvated purple complex 1 and the un-solvated dark green complex 2 is presented.

This communication presents a new terbium(III) complex that shows the highest luminescence quantum yield among the oxygen-sensitive lanthanide complexes (Φ = 0.91 under N2, Φ = 0.054 under air).

Rod-like millimetre-size crystals of a newly prepared rhodium dithionite complex with n-pentyl moieties bend upon photoirradiation and return to the initial shape upon heating; the roles of the flexible n-pentyl moieties as well as the photoreactive dithionite unit (μ-O2SSO2) are disclosed by single crystal X-ray diffraction.

This paper presents the first dysprosium(III) complex, [{(MeMeArO)3tacn}DyIII(THF)] (1Dy), that shows oxygen-sensitive luminescence. The synthesis, structure and oxygen-sensitive luminescence properties of 1Dy are reported (Φ = 0.050 and τ = 17.7 μs under N2, Φ = 0.011 and τ = 4.1 μs under O2 and KSV = 305 M−1 in THF; KSV = 0.0077%−1 in polystyrene film). The oxygen sensitive mechanism of 1Dy is discussed based on the photophysical properties of the corresponding gadolinium(III) complex, [{(MeMeArO)3tacn}GdIII(THF)].

This paper presents a 1,4,7,10-teraazacyclododecane-based tetrakis-phenol as a protonated ligand precursor and its oxygen-sensitive luminescent terbium(III) complex with an extendable phenol pendant arm (Φ = 0.91 under N2, Φ = 0.031 under air), in which the potentially N4O4-octadentate ligand unprecedentedly coordinates to the Tb3+ ion in a N4O3-heptadentate fashion.

Taking advantage of the outstanding oxygen-sensitive luminescence properties of the previously synthesised Tb(III) complex [{(MeMeArO)3tacn}LnIII(THF)] (1Tb, Ln = Tb), herein, we have prepared an oxygen sensor based on 1Tb embedded in polystyrene film (1Tb/PS) and found that 1Tb/PS shows the highest sensitivity (I0/I100 = 14.9) and the fastest response (response/recovery time = 1.9 s/2.9 s), among the lanthanide(III)-based oxygen sensors with f–f emission. Moreover, we have prepared the lanthanide(III)-based colorimetric luminescent oxygen sensor (1TbSm/PS) with green–yellow–red responses, by using 1Tb and a newly synthesised oxygen-insensitive Sm(III) complex (1Sm, Ln = Sm; Φ = 0.010 and τ = 12.2 μs).