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Materials 2021, 14, 1786 16 of 20 Materials 2021, 14, 1786 CP SmCP1 TbCP1 16 of 19 of the selection of the metal center in the preparation of luminescent CP. Regarding TbCP2 and TbCP3, only one set of data was collected since these materials were obtained using only HT synthesis. The “exchange” of the coordinated H O molecules in TbCP2 for a PL excitation band due to H2aip ligand can be proof for an e2fficient energy transfer (as- phen molecule in TbCP3 led to a significant change in the PL properties, particularly in the suming that all the emissions at the wavelength of detection come from the Ln). lifetime value. The lifetime value of TbCP3 is 6.8 times higher than that of TbCP2. 3+ TbCP2 HT 489, 543 (max), Table6.PLpeakwavTehlenSgmthsanCdPPsLhdoewcaeydpraerlaamtievterlsyonfarllrothweCemPsipssreiopnarpedeabkysHcTorarnedspMoWndAiSn.gtotheexpected transitions associated with Sm3+ (Figure 10A). PL excitation spectra and the graphical Synthesis Method λem/nm τx/μs (%)(a) τtotal(b)/μs X2(c) representations of the PL intensity in function of lifetime are included in the Supple- HT MWAS HT MWAS 590 (max), 3+ 4.43 (100) 4.43 1.015 mentary Material (Figure S7). All the Tb CP showed identical narrow emission peaks 483, 493, 518, 560, 565, 605, 642, 649, 698 (Figure10B–D),withv5e9r6y(msmax)a,lldeviationsintheemissionwavelengths(Table6),corre- 492, 545 (max), 43.82 (10.09) 185.57 1.001 sponding to the 5D → F (J = 6–2) transitions of Tb3+ ion, with the maximum peaks at 482, 492, 519, 559, 565, 605, 642, 648, 697 47J 136.121 (50.14) 545/543 and 546 nm respectively, which could be ascribed to the contribution from the by Sarma and co-workers [45], including those of lifetime values (approximately 100 μs) 278.43 (27.95) forthe1DCP.Them4o9r2e,5n45o(tmeawx)o,rthydifferencebetw12e1e.3n31t(h5e0.3C0)Pluminescencespectrais 550, 584, 589, 622, 648, 668, 680 43.662 (21.24) 148.15 1.004 5D4→7F5tran5s5i1t,i5o8n3,.5T89h,e62s2p,6e4c7,tr6a68a,6n8d0datapresentedareverysimilartothosereported 283.94 (39.76) the presence of two additional transitions for TbCP1 relative to TbCP3, corresponding to 5 7 3+ D4 → FJ (J = 1–0) transitions of the Tb 5.13 (0.50) the TbCP2 spectrum does not allow for the observation of such transitions with certainty (the verynoisypartofthespectrumiscausedbytheinstrum21e.6n2t6o(1f2t.7h6e) excitingwavelength).The 696.22 (76.77) PL excitation spectra of TbCP1 and TbCP3 (Supplementary Material: Figure S8) revealed 490, 546 (max), 0.771 (0.25) a broad band with a maximum at approximately 390 nm, which can be associated with the TbCP3 HT a PL decay measured at the maximum emission peaks of each material. Total lifetime (τtotal) of each material is given by intensity weighted 4.39 (100) 4.39 1.000 ion; on the other hand, the resolution of the 137.911 (29.53) 548, 588, 620, 647 64.737 (57.72) 80.85 1.049 586, 622, 650 25.186 (15.96) 546.99 0.975 intra-ligand transitions of the H2aip ligand, as reported in related compounds [24,45]. The 120.87 (7.02) presence of the PL excitation band due to H2aip ligand can be proof for an efficient energy (a) (b) (c) (d) Figure 10. Graphical representation of the fluorescence intensity spectra of SmCP1 (a), TbCP1 (b), TbCP2 (c) and TbCP3 Figure 10. Graphical representation of the fluorescence intensity spectra of SmCP1 (a), TbCP1 (b), TbCP2 (c) and TbCP3 (d). b lifetime.cX2indicatesthegootdrnaenssofefrth(eafsitstiunmgriensuglttsh.atalltheemissionsatthewavelengthofdetectioncomefromtheLn). (d).PDF Image | Green Chemistry with Supercritical CO2 and Enzymes
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