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Journal Name
COMMUNICATION
DOI: 10.1039/D0CC05715K
Fig. 3. Optical characterisation a) absorption and b) steady-state PL spectra of HNCPP, 1 and 2. c) Time-correlated single photon counting decays of HNCPP and 1.
2
3
A. Schneemann, V. Bon, I. Schwedler, I. Senkovska, S. Kaskel
and R. A. Fischer, Chem. Soc. Rev., 2014, 43, 6062.
L. K. Macreadie, R. Babarao, C. J. Setter, S. J. Lee, O. T.
Qazvini, A. J. Seeber, J. Tsanaktsidis, S. G. Telfer, S. R. Batten
and M. R. Hill, Angew. Chem. Int. Ed., 2020, 59, 6090.
L. K. Macreadie, E. J. Mensforth, R. Babarao, K. Konstas, S. G.
Telfer, C. M. Doherty, J. Tsanaktsidis, S. R. Batten and M. R.
Hill, J. Am. Chem. Soc., 2019, 141, 3828.
on the HNCPP ligand in DCM and DMF to accurately determine
the correct solvent medium (Figure S13). In DCM, the HNCPP
showed a rapid lifetime decay which was improved when the
solution was diluted by a factor of 10. Nevertheless, DMF was
selected as the solvent medium as DCM exhibited extensive
noise levels due to ligand aggregation.
4
The DMF ligand solution shows a monoexponential decay with
a lifetime of 2.44 ns (Fig. 3c). Photoluminescent (PL) decay, as
measured by TCSPC, shows a quenching of NCPP lifetime upon
5
6
7
8
9
G. Mínguez Espallargas and E. Coronado, Chem. Soc. Rev.,
2
018, 47, 533.
W. P. Lustig, S. Mukherjee, N. D. Rudd, A. V. Desai, J. Li and S.
K. Ghosh, Chem. Soc. Rev., 2017, 46, 3242.
II
coordination to Mn ions in 1. The quenching effect in the MOF
E. A. Dolgopolova, A. M. Rice, C. R. Martin and N. B.
Shustova, Chem. Soc. Rev., 2018, 47, 4710.
M.-L. Hu, S. A. A. Razavi, M. Piroozzadeh and A. Morsali,
Inorg. Chem. Front., 2020, 7, 1598.
T. Zhang and W. Lin, Chem. Soc. Rev., 2014, 43, 5982.
indicated electron/energy transfer processes occurring
throughout the framework structure. The PL lifetime of 1 is
biexponential with decay lifetime components of 1.55 ns,
attributed to the LMCT decay, followed by 5.30 ns. This longer,
step of PL decay is a process with a magnitude much lower than 10 Z.-H. Yan, M.-H. Du, J. Liu, S. Jin, C. Wang, G.-L. Zhuang, X.-J.
Kong, L.-S. Long and L.-S. Zheng, Nat. Commun., 2018, 9,
3353.
the fast quenching component. This step could be due to
2
5
aggregation of luminophores or the formation of long-lived
triplets due to intersystem crossing facilitated by the metal
centres in the MOF.2 To a first approximation, the PL lifetime
gives a quenching of 35% compared to the PL lifetime of the
ligand.
1
1
1 V. Stavila, A. A. Talin and M. D. Allendorf, Chem. Soc. Rev.,
2
014, 43, 5994.
6
2 P. Samanta, S. Let, W. Mandal, S. Dutta and S. K. Ghosh,
Inorg. Chem. Front., 2020, 7, 1801.
1
1
3 H.-Q. Yin and X.-B. Yin, Acc. Chem. Res., 2020, 53, 485.
4 S. Zhang, Y. Yang, Z.-Q. Xia, X.-Y. Liu, Q. Yang, Q. Wei, G. Xie,
S.-P. Chen and S.-L. Gao, Inorg. Chem., 2014, 53, 10952.
5 H.-Y. Sun, C.-B. Liu, Y. Cong, M.-H. Yu, H.-Y. Bai and G.-B. Che,
Inorg. Chem. Commun., 2013, 35, 130.
In conclusion, MOFs constructed from the HNCPP linker and
II
II
Mn or Zn result in frameworks with large pore apertures and
accessible 1D channels. Of significant interest are the
1
photophysical properties of 1, which exhibits rapid electron 16 W. Xu, Y.-J. Tang, L.-Q. Zheng, J.-M. Xu, J.-Z. Wu, Y.-C. Ou and
−
II
M.-L. Tong, Inorg. Chem., 2019, 58, 13766.
7 G. Accorsi, A. Listorti, K. Yoosaf and N. Armaroli, Chem. Soc.
Rev., 2009, 38, 1690.
transfer between the NCPP ligand and the Mn centre. Both 1
and 2 display varying degrees of network interpenetration,
1
1
providing a scaffold for strong interactions with CO
2
molecules.
8 X. Zhou, J.-L. Peng, C.-Y. Wen, Z.-Y. Liu, X.-H. Wang, J.-Z. Wu
and Y.-C. Ou, CrystEngComm, 2017, 19, 6533.
DFT-D3 investigations further highlight 1 and 2 as prime CO
2
selective candidates. These characteristics, combined with the 19 L. Martins, L. K. Macreadie, D. Sensharma, S. Vaesen, X.
Zhang, J. J. Gough, M. O'Doherty, N.-Y. Zhu, M. Rüther, J. E.
photoactivity of 1, frames future investigation into NCPP MOF
photocatalytic CO reduction.
O'Brien, A. L. Bradley and W. Schmitt, Chem. Commun.,
2
2
019, 55, 5013.
2
2
0 S. Saxer, C. Marestin, R. Mercier and J. Dupuy, Polym. Chem.,
018, 9, 1927.
1 M. O’Keeffe, M. A. Peskov, S. J. Ramsden and O. M. Yaghi,
Acc. Chem. Res., 2008, 41, 1782.
2 S. Ray and A. Das, J. Mol. Struct., 2015, 1089, 146.
3 X. Sun, Y. Ma, J. Zhao, D.-S. Li, G. Li, L. Zhang and Y. Liu,
Dalton Trans., 2018, 47, 13158.
2
Notes and references
a
f
We thank S. G. Telfer and C. Forsyth for their assistance. Part of
this research was undertaken using the MX2 beamline at the
Australian Synchrotron, part of ANSTO, and made use of the ACRF
detector. R.B acknowledges the National Computing
Infrastructure and Pawsey supercomputing facilities for the
computational resources. W.S acknowledges SFI (13/IA/1896)
and the ERC (Supramol CoG 2014–647719).
2
2
2
4 C. Altintas, G. Avci, H. Daglar, A. Nemati Vesali Azar, S.
Velioglu, I. Erucar and S. Keskin, ACS Appl. Mater. Interfaces,
2
018, 10, 17257.
2
2
5 J. Mei, Y. Hong, J. W. Y. Lam, A. Qin, Y. Tang and B. Z. Tang,
Adv. Mater., 2014, 26, 5429.
1
Z. Ji, H. Wang, S. Canossa, S. Wuttke and O. M. Yaghi, Adv.
Funct. Mater., 2020, doi.org/10.1002/adfm.202000238.
6 J. Calbo, M. J. Golomb and A. Walsh, J. Mater. Chem. A, 2019,
7
, 16571.
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