Page 3 of 5
Journal Name
ChemComm
DOI: 1C0.O10M39M/CU4CNCI0C7A25T2IOA N
voids in
2 and 3 were found to be isolated pockets. Ir(III) complexes should possess dissimilar packing structures and
Consequently, there should be negligible correlation between different solvent contents in microcrystalline and single crystalline
oxygen sensing capability and the void fraction/quality in the states, hence it should be inappropriate to predict the oxygen sensing
single crystal structures of these complexes, since complex
with low void fraction and poor channels still displays a high corresponding single crystal structures.
oxygen quenching fraction of 70.3% Moreover, the quite
analogous lifetimes of these Ir(III) complexes under N2 (1.49ꢀ
1.78 s in dilute solution, 0.16ꢀ0.37 s in microcrystalline thinꢀsolid
3
properties of these microcrystalline thinꢀfilm samples via their
.
Conclusions
µ
µ
In conclusion, we demonstrated that small molecular neutral Ir(III)
complexes are quite promising high performance microcrystalline
selfꢀinclusive oxygen sensors. Yet differed from those oxygenꢀ
sensing cationic Ru(II) and Cu(I) salts, these microcrystalline Ir(III)
complexes were found to show negligible relationship between the
oxygen quenching efficiency and the amount of void space and
quality of void channel in their single crystal structures, because the
packing structures and the solvent contents of these two crystalline
states are dissimilar. Consequently, oxygen sensing capability of
these neutral Ir(III) complexes should be carefully ascertained to
avoid the missing of hidden high performance oxygen sensing
materials.
film states, vide Table 1 and Fig. S13, S14) suggest that the
dissimilar sensing properties of 2ꢀ5 should not originate from their
different excited state lifetimes. It is noteworthy that the
emission decay data of all these thin film samples were
satisfactorily fitted using three weighted exponentials, which
seems to be contradictory to their linear SV behavior. However,
similar phenomena have also been observed by Mann et al in
porous oxygenꢀsensing Cu(I) salts,6,7b which need further inꢀ
depth investigations.
This work was supported by NSFC (Grant Nos. 21432005,
21072139, 21190031, 21177090 and 21372168) and the open fund
of the State Key Laboratory of Luminescent Materials and
Devices (South China University of Technology). We also thank
the Analytical & Testing Center, SCU for NMR measurements.
Notes and references
aKey Laboratory of Green Chemistry and Technology (Ministry of
Education), College of Chemistry, Sichuan University, Chengdu 610064,
China.
Eꢀmail:
luzhiyun@scu.edu.cn;
huangyan@scu.edu.cn;
bAnalytical and Testing Center, Sichuan University, Chengdu, 610064,
China.
cState Key Laboratory of Luminescent Materials and Devices, Institute of
Polymer Optoelectronic Materials and Devices, South China University
of Technology, Guangzhou, 510640, China.
Fig. 5 The powder Xꢀray diffraction patterns of the microcrystalline thinꢀfilm
samples (red lines: microcrystalline powder; blue lines: activated film; green lines:
asꢀprepared film;) and single crystal samples (pink lines: simulated from the
† Electronic Supplementary Information (ESI) available: Synthetic and
oxygen sensing experimentaldetails, additional spectroscoptic property
corresponding .cif files) of 2ꢀ5.
and XRD data. CCDC 1006719 for 2, 1006717 for 3 and 1006718 for 5.
For ESI and crystallographic data in CIF or other electronic format see
DOI: 10.1039/c000000x/
Consequently, differed from those cationic Ru(II) or Cu(I) salts
reported by Mann et al, the oxygenꢀsensing capability of the
microcrystalline neutral Ir(III) complexes films we reported here
could not be rationally predicted through their single crystal
structures. Hence we began to conjecture if the packing patterns
and the residue solvents of the microcrystalline samples differ
from those of the single crystal samples. Thereupon, powder Xꢀray
diffraction (PXRD) patterns of the microcrystalline powder, the asꢀ
prepared and the activated thinꢀfilm samples of 2ꢀ5 were recorded
and compared with those simulated from the corresponding .cif files
of the single crystals. As shown in Fig. 5, both the powder and the
film samples show different diffraction signals with those of their
corresponding single crystal samples, confirming that the lattice
structures within the microcrystalline film and single crystal samples
are not identical. Further thermogravimetric analysis (TGA)
indicated that the solvent contents of the activated film samples are
also quite different with those of the single crystals as well as the asꢀ
prepared ones. In fact, compared to the asꢀprepared film samples, the
activated ones all display less weight loss (Fig. S15), confirming the
occurrence of desolvation during the activation procedure. It is
noteworthy that although no solvated molecules could be found in
the single crystal lattice of 3, distinct weight loss could be observed
in 30ꢀ150 °C in both the asꢀsynthesized and activated samples of 3,
confirming the large structural difference between the single crystal
and microcrystalline film samples of 3. Accordingly, these neutral
‡ These two authors contributed equally to this work.
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