Obtaining transparent glasses made of functional coordination polymers (CPs) represents a tremendous opportunity for optical applications. In this context, the first transparent and red-emissive glasses of gold thiolate CPs have been obtained by simply applying mechanical pressure to amorphous powders of CPs. The three gold-based CP glasses are composed of either thiophenolate [Au(SPh)] n , phenylmethanethiolate [Au(SMePh)] n or phenylethanethiolate [Au(SEtPh)] n . The presence of a longer alkyl chain between the thiolate and the phenyl ring led to the formation of glass with higher transparency. The glass transitions, measured by thermomechanical analysis (TMA), occurred at lower temperature for CPs with longer alkyl chains. In addition, all three gold thiolate glasses exhibit red emission at 93 K and one of them, [Au(SMePh)] n , remains luminescent even at room temperature. An in-depth structural study of the amorphous gold thiolates by XRD, PDF and EXAFS analysis showed that they are formed of disordered doubly interpenetrated helical chains. These d10 metal-based compounds represent the first examples of transparent and luminescent CP glasses.

Diamond Light Source Ltd Diamond House Harwell Science and Innovation Campus Didcot OX11 0DE UK

Institute for Integrated Cell Material Sciences Institute for Advanced Study Kyoto University Yoshida Honmachi Sakyo ku Kyoto Japan

Institute of Experimental and Applied Physics Czech Technical University Prague CZ 11000 Prague Czech Republic

ISIS Facility STFC Rutherford Appleton Laboratory Didcot OX11 0QX UK

Univ Grenoble Alpes CNRS Institut Néel Grenoble France

Univ Lyon Université Claude Bernard Lyon 1 CNRS Institut de Recherches sur la Catalyse et l'Environnement de Lyon Villeurbanne France Email

Univ Lyon Université Claude Bernard Lyon 1 CNRS Institut Lumière Matière Villeurbanne France

Univ Lyon Université Claude Bernard Lyon 1 CNRS Laboratoire des Multimatériaux et Interfaces Villeurbanne France

Université Paris Saclay UVSQ CNRS UMR 8180 Institut Lavoisier de Versailles 78000 Versailles France

See more in PubMed

Bennett T. D., Tan J.-C., Yue Y., Baxter E., Ducati C., Terrill N. J., Yeung H. H. M., Zhou Z., Chen W., Henke S., Cheetham A. K., Greaves G. N. Nat. Commun. 2015;6:8079. PubMed PMC

Bennett T. D., Horike S. Nat. Rev. Mater. 2018;3:431.

Zhou C., Longley L., Krajnc A., Smales G. J., Qiao A., Erucar I., Doherty C. M., Thornton A. W., Hill A. J., Ashling C. W., Qazvini O. T., Lee S. J., Chater P. A., Terrill N. J., Smith A. J., Yue Y., Mali G., Keen D. A., Telfer S. G., Bennett T. D. Nat. Commun. 2018;9:5042. PubMed PMC

Frentzel-Beyme L., Kloß M., Kolodzeiski P., Pallach R., Henke S. J. Am. Chem. Soc. 2019;141:12362. PubMed

Qiao A., Tao H., Carson M. P., Aldrich S. W., Thirion L. M., Bennett T. D., Mauro J. C., Yue Y. Opt. Lett. 2019;44:1623. PubMed

Chapman K. W., Sava D. F., Halder G. J., Chupas P. J., Nenoff T. M. J. Am. Chem. Soc. 2011;133:18583. PubMed

Bennett T. D., Saines P. J., Keen D. A., Tan J.-C., Cheetham A. K. Chem.–Eur. J. 2013;19:7049. PubMed

Horike S., Chen W., Itakura T., Inukai M., Umeyama D., Asakura H., Kitagawa S. Chem. Commun. 2014;50:10241. PubMed

Nagarkar S. S., Horike S., Itakura T., Le Ouay B., Demessence A., Tsujimoto M., Kitagawa S. Angew. Chem., Int. Ed. 2017;56:4976. PubMed

Umeyama D., Horike S., Tassel C., Kageyama H., Higo Y., Hagi K., Ogiwara N., Kitagawa S. APL Mater. 2014;2:124401.

Umeyama D., Horike S., Inukai M., Itakura T., Kitagawa S. J. Am. Chem. Soc. 2015;137:864. PubMed

Bennett T. D., Yue Y., Li P., Qiao A., Tao H., Greaves N. G., Richards T., Lampronti G. I., Redfern S. A. T., Blanc F., Farha O. K., Hupp J. T., Cheetham A. K., Keen D. A. J. Am. Chem. Soc. 2016;138:3484. PubMed

Chen W., Horike S., Umeyama D., Ogiwara N., Itakura T., Tassel C., Goto Y., Kageyama H., Kitagawa S. Angew. Chem., Int. Ed. 2016;55:5195. PubMed

Lavenn C., Okhrimenko L., Guillou N., Monge M., Ledoux G., Dujardin C., Chiriac R., Fateeva A., Demessence A. J. Mater. Chem. C. 2015;3:4115.

Veselska O., Cai L., Podbevšek D., Ledoux G., Guillou N., Pilet G., Fateeva A., Demessence A. Inorg. Chem. 2018;57:2736. PubMed

Vaidya S., Veselska O., Zhadan A., Daniel M., Ledoux G., Fateeva A., Tsuruoka T., Demessence A. J. Mater. Chem. C. 2020 doi: 10.1039/d0tc01706j. DOI

Veselska O., Demessence A. Coord. Chem. Rev. 2018;355:240.

Lavenn C., Guillou N., Monge M., Podbevšek D., Ledoux G., Fateeva A., Demessence A. Chem. Commun. 2016;52:9063. PubMed

Veselska O., Okhrimenko L., Guillou N., Podbevsek D., Ledoux G., Dujardin C., Monge M., Chevrier D. M., Yang R., Zhang P., Fateeva A., Demessence A. J. Mater. Chem. C. 2017;5:9843.

Veselska O., Podbevšek D., Ledoux G., Fateeva A., Demessence A. Chem. Commun. 2017;53:12225. PubMed

Yan H., Hohman J. N., Li F. H., Jia C., Solis-Ibarra D., Wu B., Dahl J. E. P., Carlson R. M. K., Tkachenko B. A., Fokin A. A., Schreiner P. R., Vailionis A., Kim T. R., Devereaux T. P., Shen Z.-X., Melosh N. A. Nat. Mater. 2017;16:349. PubMed

Schriber E. A., Popple D. C., Yeung M., Brady M. A., Corlett S. A., Hohman J. N. ACS Appl. Nano Mater. 2018;1:3498.

Report on critical raw materials for the EU, 2017, https://ec.europa.eu/growth/sectors/raw.

Hirai Y., Nakanishi T., Kitagawa Y., Fushimi K., Seki T., Ito H., Fueno H., Tanaka K., Satoh T., Hasegawa Y. Inorg. Chem. 2015;54:4364. PubMed

Liu C., Li G., Pang G., Jin R. RSC Adv. 2013;3:9778.

Luo Z., Nachammai V., Zhang B., Yan N., Leong D. T., Jiang D.-e., Xie J. J. Am. Chem. Soc. 2014;136:10577. PubMed

Yagai S., Seki T., Aonuma H., Kawaguchi K., Karatsu T., Okura T., Sakon A., Uekusa H., Ito H. Chem. Mater. 2016;28:234.

Yoshimitsu S., Shogo Y., Masato M., Christoph W., Takashi K. Adv. Mater. 2016;28:1073. PubMed

Jin M., Seki T., Ito H. J. Am. Chem. Soc. 2017;139:7452. PubMed

Ye Z., de la Rama L. P., Efremov M. Y., Sutrisno A., Allen L. H. J. Phys. Chem. C. 2017;121:13916.

Espinet P., Lequerica M. C., Martin-Alvarez J. M. Chem.–Eur. J. 1999;5:1982.

Levchenko A. A., Yee C. K., Parikh A. N., Navrotsky A. Chem. Mater. 2005;17:5428.

Kim J.-U., Cha S.-H., Shin K., Jho J. Y., Lee J.-C. J. Am. Chem. Soc. 2004;127:9962. PubMed

Cha S.-H., Kim K.-H., Kim J.-U., Lee W.-K., Lee J.-C. J. Phys. Chem. C. 2008;112:13862.

Luo Z., Yuan X., Yu Y., Zhang Q., Leong D. T., Lee J. Y., Xie J. J. Am. Chem. Soc. 2012;134:16662. PubMed

Readman J. E., Forster P. M., Chapman K. W., Chupas P. J., Parise J. B., Hriljac J. A. Chem. Commun. 2009:3383. PubMed

Bennett T. D., Goodwin A. L., Dove M. T., Keen D. A., Tucker M. G., Barney E. R., Soper A. K., Bithell E. G., Tan J.-C., Cheetham A. K. Phys. Rev. Lett. 2010;104:115503. PubMed

Keen D. A. J. Appl. Crystallogr. 2001;34:172. PubMed PMC

Rodríguez-Carvajal J., MolPDF, 2016.

Schmidbaur H., Schier A. Chem. Soc. Rev. 2012;41:370. PubMed

Bonasia P. J., Gindelberger D. E., Arnold J. Inorg. Chem. 1993;32:5126.

Wojnowski W., Becker B., Sassmannshausen J., Peters E.-M., Peters K., von Schnering H. G. Z. Anorg. Allg. Chem. 1994;620:1417.

Dass A., Stevenson A., Dubay G. R., Tracy J. B., Murray R. W. J. Am. Chem. Soc. 2008;130:5940. PubMed

Harkness K. M., Cliffel D. E., McLean J. A. Analyst. 2010;135:868. PubMed PMC

Simpson C. A., Farrow C. L., Tian P., Billinge S. J. L., Huffman B. J., Harkness K. M., Cliffel D. E. Inorg. Chem. 2010;49:10858. PubMed PMC

Bunău O., Joly Y. J. Phys.: Condens. Matter. 2009;21:345501. PubMed

The first solid-state route to luminescent Au(I)-glutathionate and its pH-controlled transformation into ultrasmall oligomeric Au10-12(SG)10-12 nanoclusters for application in cancer radiotheraphy