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Instruments / Technical Area	Publication Details	Published	Actions
I19-Small Molecule Single Crystal Diffraction	A series of ultra-efficient blue borane fluorophores Jonathan Bould , Kamil Lang , Kaplan Kirakci , Luis Cerdán , Daniel Roca-Sanjuán , Antonio Francés-Monerris , William Clegg , Paul G. Waddell , Marcel Fuciman , Tomáš Polívka , Michael G. S. Londesborough Inorganic Chemistry 59, 17058-17070 DOI: 10.1021/acs.inorgchem.0c02277 Diamond Proposal Number(s): [22240] Show Abstract ▼ Abstract: We present the first examples of alkylated derivatives of the macropolyhedral boron hydride, anti-B18H22, which is the gain medium in the first borane laser. This new series of ten highly stable and colorless organic–inorganic hybrid clusters are capable of the conversion of UVA irradiation to blue light with fluorescence quantum yields of unity. This study gives a comprehensive description of their synthesis, isolation, and structural characterization together with a delineation of their photophysical properties using a combined theoretical and experimental approach. Treatment of anti-B18H221 with RI (where R = Me or Et) in the presence of AlCl3 gives a series of alkylated derivatives, Rx-anti-B18H22–x (where x = 2 to 6), compounds 2–6, in which the 18-vertex octadecaborane cluster architectures are preserved and yet undergo a linear “polyhedral swelling”, depending on the number of cluster alkyl substituents. The use of dichloromethane solvent in the synthetic procedure leads to dichlorination of the borane cluster and increased alkylation to give Me11-anti-B18H9Cl211, Me12-anti-B18H8Cl212, and Me13-anti-B18H7Cl213. All new alkyl derivatives are highly stable, extremely efficient (ΦF = 0.76–1.0) blue fluorophores (λems = 423–427 nm) and are soluble in a wide range of organic solvents and also a polystyrene matrix. The Et4-anti-B18H18 derivative 4b crystallizes from pentane solution in two phases with consequent multiabsorption and multiemission photophysical properties. An ultrafast transient UV–vis absorption spectroscopic study of compounds 4a and 4b reveals that an efficient excited-state absorption at the emission wavelength inhibits the laser performance of these otherwise remarkable luminescent molecules. All these new compounds add to the growing portfolio of octadecaborane-based luminescent species, and in an effort to broaden the perspective on their highly emissive photophysical properties, we highlight emerging patterns that successive substitutions have on the molecular size of the 18-vertex borane cluster structure and the distribution of the electron density within.	Nov 2020
I19-Small Molecule Single Crystal Diffraction	Macropolyhedral nickelaboranes from the metal-assisted fusion of KB9H14 Michael G. S. Londesborough , Ramón Macías , John D. Kennedy , William Clegg , Jonathan Bould Inorganic Chemistry 58, 13258-13267 DOI: 10.1021/acs.inorgchem.9b02116 Diamond Proposal Number(s): [16117] Show Abstract ▼ Abstract: The reaction of K[arachno-B9H14] with [NiCl2(dppe)] produces four new 19-vertex macropolyhedral metallaboranes that result from borane cluster fusion: [9′-(dppe)-9′-Ni-anti-B18H20] (1) and isomeric [11′-(dppe)-11′-Ni-syn-B18H20] (2), together with the chlorine-substituted derivative of 1, [5′-Cl-9′-(dppe)-9′-Ni-anti-B18H19] (3), and the 18-vertex cluster compound [7′-(dppe)-7′-anti-NiB17H21] (4). Two closo 10-vertex single-cluster species, [1-(dppe)-1-closo-NiB9H7Cl2] (5) and [1-(dppe)-1-closo-NiB9H7Cl(OH)] (6), were also isolated from the reaction. The production of the metalated syn-octadecaborane isomer 2 from the fusion of two arachno-nonaborate clusters is the first such case to be observed; in all other reported cases fusion has resulted in products with the anti-octadecaboranyl bis-nido configuration.	Sep 2019

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I19-Small Molecule Single Crystal Diffraction

A series of ultra-efficient blue borane fluorophores

Jonathan Bould , Kamil Lang , Kaplan Kirakci , Luis Cerdán , Daniel Roca-Sanjuán , Antonio Francés-Monerris , William Clegg , Paul G. Waddell , Marcel Fuciman , Tomáš Polívka , Michael G. S. Londesborough

Inorganic Chemistry 59, 17058-17070

DOI: 10.1021/acs.inorgchem.0c02277

Diamond Proposal Number(s): [22240]

Show Abstract ▼

Abstract: We present the first examples of alkylated derivatives of the macropolyhedral boron hydride, anti-B18H22, which is the gain medium in the first borane laser. This new series of ten highly stable and colorless organic–inorganic hybrid clusters are capable of the conversion of UVA irradiation to blue light with fluorescence quantum yields of unity. This study gives a comprehensive description of their synthesis, isolation, and structural characterization together with a delineation of their photophysical properties using a combined theoretical and experimental approach. Treatment of anti-B18H221 with RI (where R = Me or Et) in the presence of AlCl3 gives a series of alkylated derivatives, Rx-anti-B18H22–x (where x = 2 to 6), compounds 2–6, in which the 18-vertex octadecaborane cluster architectures are preserved and yet undergo a linear “polyhedral swelling”, depending on the number of cluster alkyl substituents. The use of dichloromethane solvent in the synthetic procedure leads to dichlorination of the borane cluster and increased alkylation to give Me11-anti-B18H9Cl211, Me12-anti-B18H8Cl212, and Me13-anti-B18H7Cl213. All new alkyl derivatives are highly stable, extremely efficient (ΦF = 0.76–1.0) blue fluorophores (λems = 423–427 nm) and are soluble in a wide range of organic solvents and also a polystyrene matrix. The Et4-anti-B18H18 derivative 4b crystallizes from pentane solution in two phases with consequent multiabsorption and multiemission photophysical properties. An ultrafast transient UV–vis absorption spectroscopic study of compounds 4a and 4b reveals that an efficient excited-state absorption at the emission wavelength inhibits the laser performance of these otherwise remarkable luminescent molecules. All these new compounds add to the growing portfolio of octadecaborane-based luminescent species, and in an effort to broaden the perspective on their highly emissive photophysical properties, we highlight emerging patterns that successive substitutions have on the molecular size of the 18-vertex borane cluster structure and the distribution of the electron density within.

Nov 2020

I19-Small Molecule Single Crystal Diffraction

Macropolyhedral nickelaboranes from the metal-assisted fusion of KB9H14

Michael G. S. Londesborough , Ramón Macías , John D. Kennedy , William Clegg , Jonathan Bould

Inorganic Chemistry 58, 13258-13267

DOI: 10.1021/acs.inorgchem.9b02116

Diamond Proposal Number(s): [16117]

Show Abstract ▼

Sep 2019

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