A Highly Stable 3D Luminescent IndiumâPolycarboxylic Framework

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A Highly Stable 3D Luminescent Indium−Polycarboxylic Framework for the Turn-off Detection of UO22+, Ru3+, and Biomolecule Thiamines Ning Du, Jian Song, Shuang Li, Yu-Xian Chi, Feng-Ying Bai, and Yong-Heng Xing* College of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, P.R. China S Supporting Information *

ABSTRACT: Hydrothermal reaction of the multidentate organic ligand (H6TTHA) with indium chloride (InCl3) produced a highly stable 3D luminescent indium-organic framework [In2(OH)2(H2TTHA)(H2O)2]n (1). Complex 1 exhibits remarkable luminescent properties, especially the multifunction sensitivity and selectivity for detecting Ru3+, UO22+; as well as small biomolecules thiamines (TPP, TMP, and TCl) based on a “turn-off” manner. In particular, the pyrophosphate groups of TPP and the phosphate groups of TMP could further affect the quenching rate, leading to different luminescent responds. In addition, we also discussed and proved the luminescence quenching mechanism in detail through comparative test and PXRD characterization. Therefore, complex 1 could be used as a kind of excellent luminescence sensor to detect Ru3+, UO22+, and thiamines (TPP, TMP, and TCl). KEYWORDS: indium complexes, 1,3,5-triazine-2,4,6-triamine hexaacetic acid (H6TTHA), metal ions, thiamines, luminescent sensing

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INTRODUCTION Self-assembled metal−organic frameworks (MOFs)1−6 were broadly studied previously as fascinating function materials for potential applications in numerous areas, such as gas storage and separation,7−14 magnetism,15−17 drug delivery and biomedical imaging,18,19 heterogeneous catalysis,20−24 optoelectronics (nonlinear optics),25,26 energy storage and conversion, etc.27−29 However, the selected metals (or metal centers) are generally limited to transition metal and lanthanide, sometimes Na + and Mg2+. Because tris(8hydroxyquinolinolato)aluminum(III) are widely used in organic light-emitting diodes (OLEDs),30 the rational exploration of the luminescent materials containing IIIA group metals (M = B, Al, Ga, In) has attracted more interest.31−35 Among the IIIA group elements, indium possesses excellent prospects considering of the structural diversity and abundant electron transport, which can produce chelates of high luminous efficiency with the capacity of emitting different colors. Nevertheless, a few kinds of high-dimensional indium−organic frameworks (InOFs) have been reported, it is always a great challenge to obtain In(III) complexes of kinetically stable, because In(III) metal salt is in a strong tendency to hydrolyze in the synthesis process.34−36 Therefore, more effort must be © XXXX American Chemical Society

devoted to designing and constructing functional InOFs materials in the future. Recently, the development of luminescent MOFs (LMOFs) as chemical sensors for ions and small molecules (such as Cu2+, Pd2+, Fe3+, Hg2+, F−, CN−, I−, explosive, etc.) has become a hot topic in the research area of the coordination polymer materials, because these target analytes play a crucial role in chemical, environmental, and biological processes.37−42 And yet, there are still many important chemical substances need to be detected and analyzed systematacially. For instance, heavy metal uranium pollution has become a global problem, uranium of trace amounts can also showed great toxicity. As the most common uranium species in aqueous solution, the environmental chemistry of UO22+ is crucial to study extensively because of the rapid development of nuclear energy around the world, especially in the respect of manufacture weapons.43−45 In addition, ruthenium as one of the platinum group metals is widely used in electronic industry, chlor-alkali industry, automobile industry, and other fields. In the meantime, Grubbs Received: August 4, 2016 Accepted: October 10, 2016

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DOI: 10.1021/acsami.6b09456 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

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ACS Applied Materials & Interfaces

being stirred for 1 h, the resulting solution was placed to a 23 mL reactor and heated statically at 160 °C for 72 h, then slow cooling to room temperature. Colorless crystals of complex 1 were acquired after filter and wash thoroughly with deionized water. Yield: 60% (based on InCl3), Anal. Calcd. for C15H20N6O16In2 (770.01): C, 23.40; H, 2.62; N, 10.92%. Found: C, 23.50; H, 2.68; N, 10.83%. IR data (KBr, cm−1): 3605 (ν(O−H)); 3109 (ν(CH)); 2978, 2940 (ν(−CH3)); 1717 (νs(CO)); 1556, 1480 (ν(CN/CC)); 1240 (νas(CO)). X-ray Crystallographic Determination. A suitable single crystal of complex 1 was seated on the glass fiber for structure determination. Reflection data were obtained at 298 K on a Bruker AXS SMART APEX II CCD diffractometer with Mo−Kα radiation (λ = 0.71073 Å). A semiempirical absorption correction was adopted using program SADABS.52 Program SHELXTL-97 was used to check crystal-cell parameter (XPREP), crystal structure was solved by the direct method (XS) and least-squares refinement (XL).53 All of non-hydrogen atoms were refined anisotropically. Hydrogen atoms on carbon were found by calculated positions. Hydrogen atoms on coordinated H2O were introduced in Fourier map. Reflection data and details of structure refinement are listed in Table 1. Selected bond lengths and angles for complex 1 are given in Table S1.

catalyst as one of the important containing ruthenium catalysts is widely used in many fields, such as chemical engineering, environment, medicine, etc. Among medical science, ruthenium(II/III) has exhibited significant biological activity, including antimicrobial activity and its well-known interaction with DNA.46,47 Furthermore, thiamine, also known as vitamin B1 (antineuritic vitamin or antiberiberi vitamin), is necessary for energy metabolism in human body, especially the metabolism of sugar. Thiamine has been widely studied, in which it is related to the biologically catalytic processes. For instance, thiamine pyrophosphate (TPP) could be used as a kind of coenzyme like others biological enzymes (such as oxidoreductase, transferases, hydrolases, etc.).48,49 Although these substances mentioned above show paramount importance both for the environment and health, unfortunately, luminescent MOFs materials used in the detection of thiamine pyrophosphate has seldom been reported up to now.50 Herein, a highly stable self-assembled 3D luminescent InOF was obtained for the first time, namely [In2(OH)2(H2TTHA)(H2O)2]n (1), based on the flexible hexapodal polycarboxylate ligand (H6TTHA), as shown in Scheme 1. As far as we know,

Table 1. Crystallographic Data for Complex 1 complex chemical formula M (g mol−1) cryst syst space group a (Å) b (Å) c (Å) V (Å3) Z Dcalcd (g·cm−3) cryst size (mm3) F(000) μ(Mo−Kα) (mm−1) θ (deg) no. of reflns collected no. of independent reflns params Rint Δ(ρ) (e Å−3) GOF Ra wR2a

Scheme 1. Structure of H6TTHA

the crystal structures of indium complexes with the H6TTHA ligand have never been reported up to now. In addition, the coordination mode of H6TTHA in this work was observed first. Expectedly, the framework of complex 1 exhibits satisfactory luminescent properties, and we focus on the systematic detections of metal ions (Ru3+ and UO22+) and thiamines (TPP, TMP,, and TCl). Furthermore, the sensing mechanisms for metal ions (Ru3+ and UO22+) and thiamines (TPP, TMP and TCl) are also investigated carefully.

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EXPERIMENTAL SECTION

1 C15H20N6O16In2 770.01 orthorhombic Pbcn 4.9551(8) 22.122(4) 20.757(3) 2275.3(6) 4 2.248 0.24 × 0.15 × 0.09 1512 2.124 1.84−27.43 12596 2589 (2069) 179 0.0340 0.753 and −0.888 1.015 0.0268 (0.0640)b 0.0390 (0.0687)b

R = Σ ||Fo | − |Fc ||/ Σ |Fo |; wR2 = [Σw(Fo2 − Fc2)2/Σw(Fo2)2]1/2; |Fo | > 4σ(|Fo |). bBased on all data. a

Materials and Methods. The chemicals used were reagent grade or better. PerkinElmer 240C automatic analyzer was used to conduct elemental analyses of C, H, and N. Bruker AXS TENSOR-27 FT-IR spectrometer was used to measure IR spectra in the scope of 400− 4000 cm−1 at 298 K with pressed KBr pellets. JASCO V-570 UV/vis/ NIR microspectrophotometer (200−2500 nm) was used to record UV−vis-NIR spectra of complex 1 and H6TTHA. Thermal gravimetric analyses (TGA) were obtained based on a PerkinElmer Diamond TG/ DTA under atmosphere from 25 to 1000 °C with a heating rate of 10 °C/min. Powder X-ray diffraction pattern (PXRD) was performed on a Bruker Advance-D8 equipped with Cu Kα radiation in the scope of 5° < 2θ < 55°, with a step size of 0.02° (2θ) and a count time of 2 s per step. JASCO FP-6500 spectrofluorimeter was used to measure luminescence spectra of complex 1 and H6TTHA both solid samples ad emulsions at 298 K. Synthesis. H6TTHA was synthesized on the basis of the method in related literature.51 [In2(OH)2(H2TTHA)(H2O)2]n (1). A mixture of InCl3 (0.022 g), H6TTHA (0.024 g), and demineralized water (6 mL) was placed in a conical flask. HNO3 (4 M) was dropwise added to adjust pH. After

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RESULTS AND DISCUSSION [In2(OH)2(H2TTHA)(H2O)2]n (1). Complex 1 possesses a 3D network framework, which crystallizes in the orthorhombic space group Pbcn. The molecular structure contain a In3+, an half of deprotonated H2TTHA4−, a μ2−OH and a coordinated H2O (Figure 1a). Every central In3+ ion is hexa-coordinate by carboxyl oxygen atoms (O1, O5C, O6A) from three H2TTHA4− ligands, hydroxyl oxygen atoms (O7, O7B), and O8 come from coordinated H2O, to form a slightly distorted [In(μ2-O)2O4] square bipyramid geometry. The In−O distance is 2.109(2)−2.205(2) Å, through checking published literature, the average value about 2.42 Å.54−56 For the H6TTHA ligand, lots of coordination modes have been continually reported, as shown in Table S2.57−68 Surprisingly, the H6TTHA ligand in B


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Figure 1. Structure of complex 1: (a) In3+ ion environment of complex 1; (b) coordination mode of H2TTHA4−; (c) one-dimensional chain along the a-axis; (d) 3D network structure constructed from the [In2O2] SBUs; (e) simplified way of the ligand, SBU, and the topological presentations of the 3D framework structure. (Green and pink balls represent the dimeric [In2O2] SBU and the triazine ring center of the H2TTHA4−, respectively.) Hydrogen atoms have been omitted. Symmetric codes: A = 2.5 − x, 0.5 + y, z; B = 2 − x, 1 − y, −z; C = 1.5 − x, 0.5 + y, z; D = 0.5 + x, 0.5 − y, −z; E = −0.5 + x, 0.5 − y, −z; F = 2 − x, y, 0.5 − z.

Figure 2. Luminescence spectra of the H6TTHA (λex = 262 nm) and complex 1 (λex = 271 nm) at room temperature.

complex 1 reported herein exhibits distinctly unique coordination mode.57 The 4-fold deprotonated H2TTHA4− ligand connects six In3+ ions (μ6-bridge) through syn−anti bridging and monodentate carboxylate moieties (Figure 1b). In addition, the ligand exhibits a molecular symmetry of C2(2) in the crystal lattice, which passes through the atoms N2, C8 and N3. The adjacent two pairs of arms are connected by atoms (N1, N1F), which are placed on the top and the bottom of the triazine ring. And the other pair of arms are connected by atom N2 in the opposite direction of the triazine plane. In the extended structure, the In3+ ion is bridged by the hydroxyl oxygen atoms into a dimeric [In2O2] SBU (“secondary” building unit), further

Figure 3. (a) Luminescence emission spectra of complex 1 in different metal ions emulsions at room temperature (C1 on behalf of complex 1); (b) corresponding histogram to compare the emission peak intensity of complex 1 and 1@Mn+.

C


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Figure 4. Luminescence emission spectra of 1@Mn+ emulsions with the concentration range of metal ions from 0.001 to 10000 μM: (a) for 1@Ru3+; (b) 1@(UO2)2+.

forming a 1D chain in the direction of a-axis through bridging carboxylate groups of the ligands (Figure 1c). Finally, the flexible ligand connects these 1D chains to form an intriguing 3D network structure (Figure 1d). For the purpose of confirm connection method between H6TTHA and In3+ ion, the topology of complex 1 (InOF) was investigated earnestly. The [In2O2] SBU and the triazine ring center were regarded as nodes, complex 1 could be explained topologically as an unique three-dimensional (6,6)-connect 2-nodal network with a Schläfli symbol of (412.63)(49.66) (Figure 1e). UV−Vis Spectra, IR Spectra, and Thermal Gravimetric Analyses. The UV−vis spectra for complex 1 and the H6TTHA ligand were collected. As shown in Figure S1, the absorption bands of 216, 245, and 313 nm for complex 1 are associated with the n → π* and π → π* transition of H6TTHA. The IR spectra of complex 1 are listed in Figure S2. Thermal gravimetric analyses (TGA) were measured for complex 1 to investigate its thermal stability (Figure S3). The complex 1 exhibits a weight loss (obsd: 8.85%), which takes place between 240 and 295 °C, which relevant two hydroxyl groups and two coordinated H2O were lost (calcd: 9.09%). Then, the framework begins to collapse with a main process from 295 to 900 °C, corresponding to the total decomposition of H2TTHA4− ligand (obsd: 60.92%; calcd: 61.04%). The complex 1 finally transformed to the residue of the In2O3 phase. Luminescence Property. Luminescence spectra of complex 1 and H6TTHA were measured at 298 K. Upon the excitation wavelength of 262 nm (Figure 2), H6TTHA in solid state exhibits an emission band at 374 nm, which should belong to π* → n and π* → π transitions. Compared to the free H6TTHA ligand, complex 1 shows a slightly blue-shift emission

Figure 5. Corresponding bar diagram showing the (I0/I − 1) of 1@ Mn+ (monitored at 350 nm) in the concentration ranges of analytes from 0.001 to 10000 μM: (a) for 1@Ru3+; (b) for 1@UO22+.

Scheme 2. Molecular Structures of Thiamines (TPP, TMP, and TCl)

band at 365 nm in the solid state (λex = 271 nm). Usually, it is well-known that the metal center has no unpaired electron, particularly the metal center that has d10 configuration, which could produce a stronger linker-based emission peak. The luminescence performance of complex 1 is also likely linkerbased because of the emission peak position is close to that of the free H6TTHA. The phenomenon of the obvious blue-shift D


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Figure 7. Corresponding three-dimensional histogram to compare the emission peak intensity of 1 and 1@thiamine.

Figure 8. (a−c) Corresponding bar diagram showing the I0/I of 1@ thiamines monitored at 350 nm in the concentration ranges of analytes from 0.001 to 10000 μM. Figure 6. (a−c) Luminescence emission spectra of 1@thiamines emulsions and (d) luminescence quenching efficiencies with the concentration range of thiamines from 0.001 to 10000 μM.

may be due to the strong covalent interaction between In3+ cation and the H2TTHA4− anion. E


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For further revealed luminescent sensitivity and selectivity of complex 1, quenching constants (KSV) were quantified by Stern−Volmer equation I0/I = KSV[Q] + 1

(1)

Including I0, original luminescence intensity of complex 1, I, luminescence intensity of 1@Mn+; [Q], molarity of matel ions (Ru3+ and UO22+); and KSV (quenching constant), which could be used to quantitative evaluate complex 1 as the candidate material of metal ion (Ru3+ and UO22+) sensors. I0/I presents linear proportional relationship with molarity of metal ions (Ru3+ and UO22+), the slope is KSV (quenching constant). As shown in Figure 5, corresponding bar diagram showing the (I0/ I − 1) of 1@Ru3+ and 1@UO22+ (monitored at 350 nm) in the concentration ranges of analytes (from 0.001 to 10000 μM). The quenching constant (KSV) was 4.2 × 104 M−1 for Ru3+, 4.8 × 104 M−1 for UO22+. The larger KSV value indicated excellent sensitivity and selectivity, which made complex 1 become a typical luminescent probe for detecting Ru3+ and UO22+ ions. For further explanation, the luminescent quenching mechanism, the PL spectra of pure UO2(CH3COO)2 aqueous solution with different concentration in the range from 0.001 to 10000 μM are measured, as shown in Figure S4. By comparing the emission peak intensity of the relative concentration, there is sure to be some weak interaction between UO22+ and complex 1 (InOF), resulting in energy transfer or decay. It may be that the UO22+ cations are adsorbed on the surface of InOFs to form hydrogen-bond interactions or weak coordination bonds with free carboxylate groups. For 1@ Ru3+ emulsions, the luminescence quenching mechanism is difficult to explain clearly at this moment. As is known to all, Ru3+ cations prefer N to O donors in coordination capability. Thus, we speculate that weak binding between the nitrogen atoms of amine from N−diacetate groups and Ru3+ in the 1@ Ru3+ was formed, which emerges from energy transfer and nonradiative decay. There are two main reasons for above phenomenon: (i) the metal ions (Ru3+ and UO22+) have higher nuclear charge number and more empty orbits, and thus have better ability to accept feedback electrons from the ligands; (ii) complex 1 and the metal ions (Ru3+ and UO22+) in the water solution could have similar matching energy levels of the excited state, producing energy transfer. Others metal ions do not have the above characteristics simultaneously. According to the above phenomenon, we found that complex 1 can be used as a kind of hopeful luminescence probe to detect metal ions (Ru3+ and UO22+). Sensing Properties for Thiamines. In the view of the superior sensing properties for detecting metal ions (Ru3+ and UO22+), we further investigated the luminescent sensing properties for detecting small biomolecules thiamine (vitamin B1). Herein, to study the sensing mechanism more systematically, we selected three kinds of thiamines (TPP, TMP, and TCl), i.e., thiamine hydrochloride (TCl, i), thiamine monophosphate (TMP, ii), and thiamine pyrophosphate (TPP, iii) (Scheme 2), as the typical vitamin B1 were selected for experiments according to the method above. Expectedly, complex 1 displays the most obvious quenching effect in all of the three kinds of thiamines emulsions with the concentration of 1.0 M (Figure S5). On the basis of the reaction phenomena, we prepared 1@TPP, 1@TMP and 1@ TCl emulsions with the concentration range of thiamines (TPP, TMP, and TCl) from 0.001 to 10000 μM, respectively, for measured their luminescence spectra. The luminescence

Figure 9. PXRD pattern of the simulated data and the experimental data of complex 1, respectively.

Sensing Properties for Metal Ions. To examine the potential of complex 1 toward detection of metal ions, we investigated its luminescent properties in different metal ions emulsions. The samples (3 mg) were ground down and immersed into the corresponding H2O solutions (4 mL) containing various kinds of metal salts (0.02 mmol) (M = NaCl, Mg(CH3COO)2, KI, FeSO4, Co(NO3)2, Ni(NO3)2, Cu(NO 3 ) 2 , ZnSO 4 , RuCl3 , Cd(NO3 ) 2 , Eu(NO3 ) 3 , and UO2(CH3COO)2, respectively). After ultrasonic oscillation for 30 min, the mixtures containing metal ions and complex 1 form emulsions. The photoluminescent properties of 1@Mn+ and the pure complex 1 are recorded and compared in Figure 3. It is clearly found that the PL peak position in emulsions has been altered for near 15 nm, which is compared with complex 1 in the solid state. Such luminescent variation phenomenon is mainly due to the solvent effect.33,69,70 For the emission intensity, only 1@RuCl3 and 1@UO2(CH3COO)2 exhibit the most significant quenching effect, whereas other metal ions enhance or weaken the emission intensity at different degrees mildly. For the 1@UO2(CH3COO)2, additional weaker peaks appear at around 515 nm, which should be assigned to the characteristic emissions peak of UO22+. According to the experiment, these results also indicate that the impact of anions (Cl−, I−, CH3COO−, SO42−, NO3−) could be neglected. Complex 1 was immersed into Ru3+/H2O and UO22+/H2O solutions, respectively, containing different concentrations of Ru3+ and UO22+ ions for further studying luminescent response. Predictably, the luminescent intensities of 1@Ru3+ and 1@ UO22+ rely mainly on the concentration of the adding metal ions (Ru3+ and UO22+), which decrease proportionally in the concentration range from 0.001 to 10000 μM (Figure 4). For 1@UO22+ emulsions, it is worth mentioning that the characteristic emissions peaks of UO22+ ion in the PL spectra exhibit an unusual regularity. The emission peak intensity increased first and then decreased gradually with increasing the concentration of UO22+ ion, where the strongest point appears near 100 μM. In addition, the main emission peak of 1@UO22+ has a obvious blue shift phenomenon, which reveals that there may be the energy transfer between UO22+ and 1 (InOF). At the concentration of 10000 μM, the highly quenching efficiency is 100% for Ru3+ and 99.8% for UO22+ compare to the initial luminescence intensity, respectively. The detection limits of 1 for metal ions (Ru3+ and UO22+) are 0.26 ppm for Ru3+, 0.42 ppm for UO22+. F


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phosphate groups of the TMP could further affect the quenching rate through the rich O or OH donors forming more hydrogen bond interactions with the host framework easily. Therefore, our results show that complex 1 may be an excellent candidate material for a luminescence probe that has multifunctional sensitivity and selectivity to detect Ru3+, UO22+, and thiamines.

intensity gradually decreases with increasing thiamines concentration (Figure 6). However, the quenching efficiencies of the three kinds of thiamines emulsions are obvious different, in which the order of quenching efficiencies is 99.4% for 1@ TPP > 88.9% for 1@TMP > 73.3% for 1@TCl, when the thiamines concentration is 1000 μM. The corresponding histogram is shown that the emission peak intensity (recorded at 350 nm) for complex 1 and 1@ thiamine (Figure 7). The detection limits of complex 1 for thiamine are 0.46 ppm for TPP, 0.38 ppm for TMP, and 0.33 ppm for TCl, respectively. On the basis of eq 1, I0/I presents a linear proportional relationship with molarity of thiamine (TPP, TMP, and TCl), and the slope is KSV. As shown in Figure 8, corresponding bar diagram showing the (I0/I) of 1@TPP, 1@TMP and 1@TCl (monitored at 350 nm) in the concentration ranges of analytes (from 0.001 μM to 10000 μM). The quenching constant (KSV) for TPP, TMP, and TCl was 3.6 × 106 M−1, 1.0 × 104 M−1, and 2.9 × 103 M−1, respectively. The greater KSV value indicated excellent sensitivity and selectivity, which made complex 1 become a typical luminescent probe for detecting thiamines. The luminescence quenching mechanism can be attributed to energy transfer and nonradiative decay between guest (thiamines) and host (complex 1). The above reasoning suggests that the possibility of excitation light was absorbed through guest molecules (thiamines), also have the possibility of electrons transfer from excitation level of complex 1 to lower excitation level of guest molecules. Moreover, the pyrophosphate groups of the TPP and the phosphate groups of the TMP containing more O- or OH- donors may form hydrogen bond interactions with the host indium−organic framework easily. Therefore, the pyrophosphate groups of the TPP and the phosphate groups of the TMP should be the main factor leading to the difference of the quenching rate by comparing the structure of TPP, TMP, and TCl. The explorations of luminescent sensing properties indicate that complex 1 is one of the best candidate materials of sensitive InOFs probe to detect TPP, TMP, and TCl. PXRD Analyses. For further exploring the luminescence quenching mechanism, PXRD analyses data were gained and compared to simulate pattern, as shown in Figure 9. It was reveal that the framework of complex 1 after immersion is stable yet, following possibilities were eliminated: (i) collapse of the framework; (ii) metal ions exchange between coordination polymers and added metal ions. Thus, weak interaction between guest and host (InOF) is the most likely cause resulting in luminescent quenching phenomenon.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.6b09456. Selected bond lengths and angles of complex 1; seven types of conformations with 24 kinds of coordination modes for reported H6TTHA; UV−vis and IR spectra; TGA; the luminescence spectra of pure UO2(CH3COO)2 solution, 1@TPP, 1@TMP, and 1@ TCl emulsions. (PDF) CIF file for complex 1 (also available at Cambridge Crystallographic Database Centre (http://www.ccdc. cam.ac.uk) CCDC 1444237) (CIF)

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by National Natural Science Foundation of China (Grants 21371086 and 21571091) and Commonweal Research Foundation of Liaoning province in China (Grant 2014003019).

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REFERENCES

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CONCLUSIONS In general, a highly stable 3D luminescence InOF under hydrothermal condition using a flexible poly(carboxylic acid) (H6TTHA) was obtained successfully, which is the first crystal structure combining metal indium with the H6TTHA so far. In addition, the coordination mode of H6TTHA was observed first. Interestingly, complex 1 exhibits an attractive sensing ability toward various metal cations (Ru3+ and UO22+) based on a “turn-off” manner. Furthermore, complex 1 also exhibits a highly sensitivity to detect different of thiamines (TPP, TMP, TCl). The luminescence quenching mechanism for metal ions (Ru3+ and UO22+) as well as three kinds of thiamines can be attributed to the interactions (hydrogen bond interactions) or weak binding between the guest metal ions, thiamines, and the host framework emerging energy transfer and/or nonradiative decay. Strikingly, the pyrophosphate groups of the TPP and the G


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