The objective of this work was the exploration of the effect of the second coordination sphere on the magnetic properties of [Ln(NO3)3(H2O)3]·(18C6) (Ln = Dy (1) and Er (2)) compounds comprising co-crystallized 18-crown-6 ethers. Both compounds were identified as field-induced single molecule magnets (SMMs) with estimated magnetization reversal barriers U eff = 66-71 K for 1 and U eff = 21-24 K for 2. Theoretical calculations with the B3LYP functional revealed substantial change and redistribution of the electrostatic potential upon accounting for the second coordination sphere represented by two 18C6 molecules, which resulted in the change of the crystal-field around metal atoms. As a result, the multireference CASSCF calculations exposed significant impact of the second coordination sphere on the energy splitting of the respective 6 H 15/2 (DyIII) and 4 I 15/2 (ErIII) ground states, the magnetization reversal barrier and the magnetic anisotropy parameters. Moreover, the calculated magnetization reversal barriers, U calc. = 57 K for 1 and U calc. = 16 K for 2, are in good agreement with the experimental values accentuating the importance of the second coordination sphere on the magnetic properties of SMMs.

Department of Inorganic Chemistry Faculty of Science Palacký University 17 Listopadu 12 CZ 771 46 Olomouc Czech Republic

Regional Centre of Advanced Technologies and Materials Faculty of Science Palacký University Šlechtitelů 27 CZ 783 71 Olomouc Czech Republic

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Ishikawa N. Sugita M. Ishikawa T. Koshihara S. Kaizu Y. J. Am. Chem. Soc. 2003;125:8694–8695. doi: 10.1021/ja029629n. PubMed DOI

Sessoli R. Hui L. Schake A. R. Wang S. Vincent J. B. Folting K. Gatteschi D. Christou G. J. Am. Chem. Soc. 1993;115:1804–1816. doi: 10.1021/ja00058a027. DOI

Sessoli R. Gatteschi D. Caneschi A. Novak M. A. Nature. 1993;365:141–143. doi: 10.1038/365141a0. DOI

Gatteschi D., Sessoli R. and Villain J., Molecular Nanomagnets; Oxford University Press, Oxford, 2006

Molecular Magnets Physics and Applications, ed. J. Bartolomé, F. Luis and J. F.Fernández, Springer-Verlag, Berlin, Heidelberg, 2014

Warner B. Hallak F. E. Prüser H. Sharp J. Persson M. Fisher A. J. Hirjibehedin C. F. Nat. Nanotechnol. 2015;10:259–263. doi: 10.1038/nnano.2014.326. PubMed DOI

Ardavan A. Rival O. Morton J. J. L. Blundell S. J. Tyryshkin A. M. Timco G. A. Winpenny R. E. P. Phys. Rev. Lett. 2007;98:057201. doi: 10.1103/PhysRevLett.98.057201. PubMed DOI

Leuenberger M. N. Loss D. Nature. 2001;410:789–793. doi: 10.1038/35071024. PubMed DOI

Bogani L. Wernsdorfer W. Nat. Mater. 2008;7:179–186. doi: 10.1038/35071024. PubMed DOI

Woodruff D. N. Winpenny R. E. P. Layfield R. A. Chem. Rev. 2013;113:5110–5148. doi: 10.1021/cr400018q. PubMed DOI

Zhang P. Guo Y.-N. Tang J. Coord. Chem. Rev. 2013;257:1728–1763. doi: 10.1016/j.ccr.2013.01.012. DOI

Pointillart F. Cador O. Le Guennic B. Ouahab L. Coord. Chem. Rev. 2017;346:150–175. doi: 10.1016/j.ccr.2016.12.017. DOI

Dey A. Kalita P. Chandrasekhar V. ACS Omega. 2018;3:9462–9475. doi: 10.1021/acsomega.8b01204. PubMed DOI PMC

Long J. Habib F. Lin P.-H. Korobkov I. Enright G. Ungur L. Wernsdorfer W. Chibotaru L. F. Murugesu M. J. Am. Chem. Soc. 2011;133:5319–5328. doi: 10.1021/ja109706y. PubMed DOI

Rinehart J. D. Long J. R. Chem. Sci. 2011;2:2078–2085. doi: 10.1039/C1SC00513H. DOI

Liu J. Chen Y.-C. Liu J.-L. Vieru V. Ungur L. Jia J.-H. Chibotaru L. F. Lan Y. Wernsdorfer W. Gao S. Chen X.-M. Tong M.-L. J. Am. Chem. Soc. 2016;138:5441–5450. doi: 10.1021/jacs.6b02638. PubMed DOI

Ding Y.-S. Chilton N. F. Winpenny R. E. P. Zheng Y.-Z. Angew. Chem., Int. Ed. 2016;55:16071–16074. doi: 10.1002/anie.201609685. PubMed DOI

Guo F. Day B. M. Chen Y. Tong M. Mansikkamäki A. Layfield R. A. Angew. Chem., Int. Ed. 2017;56:11445–11449. doi: 10.1002/anie.201705426. PubMed DOI

Goodwin C. A. P. Ortu F. Reta D. Chilton N. F. Mills D. P. Nature. 2017;548:439–442. doi: 10.1038/nature23447. PubMed DOI

Guo F.-S. Day B. M. Chen Y.-C. Tong M.-L. Mansikkamäki A. Layfield R. A. Science. 2018:eaav0652. PubMed

Jiang S.-D. Wang B.-W. Sun H.-L. Wang Z.-M. Gao S. J. Am. Chem. Soc. 2011;133:4730–4733. doi: 10.1021/ja200198v. PubMed DOI

Chen S.-M. Xiong J. Zhang Y.-Q. Yuan Q. Wang B.-W. Gao S. Chem. Sci. 2018;9:7540–7545. doi: 10.1039/C8SC01626G. PubMed DOI PMC

Meng Y.-S. Wang C.-H. Zhang Y.-Q. Leng X.-B. Wang B.-W. Chen Y.-F. Gao S. Inorg. Chem. Front. 2016;3:828–835. doi: 10.1039/C6QI00028B. DOI

Carlin R. L., Magnetochemistry, Springer-Verlag, Berlin, 1986

Escalera-Moreno L. Baldoví J. J. Gaita-Ariño A. Coronado E. Chem. Sci. 2018;9:3265–3275. doi: 10.1039/C7SC05464E. PubMed DOI PMC

Ding Y.-S. Yu K.-X. Reta D. Ortu F. Winpenny R. E. P. Zheng Y.-Z. Chilton N. F. Nat. Commun. 2018;9:3134. doi: 10.1038/s41467-018-05587-6. PubMed DOI PMC

Pettinari C., Marchetti F. and Drozdov A., in Comprehensive Coordination Chemistry II, 2003, vol. I, pp. 211–246

Edelmann F. T. Coord. Chem. Rev. 2014;261:73–155. doi: 10.1016/j.ccr.2013.11.008. DOI

Hardie M. J. Raston C. L. J. Chem. Soc., Dalton Trans. 2000;15:2483–2492. doi: 10.1039/B002047H. DOI

Nishihara S. Akutagawa T. Hasegawa T. Nakamura T. Inorg. Chem. 2003;42:2480–2482. doi: 10.1021/ic026204t. PubMed DOI

Petrosyants S. Dobrokhotova Z. Ilyukhin A. Efimov N. Mikhlina Y. Novotortsev V. Inorg. Chim. Acta. 2015;434:41–50. doi: 10.1016/j.ica.2015.05.014. DOI

Wada H. Ooka S. Yamamura T. Kajiwara T. Inorg. Chem. 2016;56:147–155. doi: 10.1021/acs.inorgchem.6b01764. PubMed DOI

Ding Y.-S. Han T. Hu Y.-Q. Xu M. Yang S. Zheng Y.-Z. Inorg. Chem. Front. 2016;3:798–807. doi: 10.1039/C5QI00308C. DOI

Maxwell L. Amoza M. Ruiz E. Inorg. Chem. 2018;57:13225–13234. doi: 10.1021/acs.inorgchem.8b01688. PubMed DOI

Peng G. Zhang Y.-Y. Li Z.-Y. Inorg. Chem. Commun. 2017;77:40–43. doi: 10.1016/j.inoche.2017.01.031. DOI

Mamontova E. Long J. Ferreira R. Botas A. Luneau D. Guari Y. Carlos L. Larionova J. Magnetochemistry. 2016;2:41. doi: 10.3390/magnetochemistry2040041. DOI

Petit S. Pilet G. Luneau D. Chibotaru L. F. Ungur L. Dalton Trans. 2007:4582–4588. doi: 10.1039/B708926K. PubMed DOI

Rogers R. D. Rollins A. N. J. Chem. Crystallogr. 1994;24:321–329. doi: 10.1007/BF01670208. DOI

Pinsky M. Avnir D. Inorg. Chem. 1998;37:5575–5582. doi: 10.1021/ic9804925. PubMed DOI

Ruiz-Martínez A. Casanova D. Alvarez S. Chem. - Eur. J. 2008;14:1291–1303. doi: 10.1002/chem.200701137. PubMed DOI

Ruiz-Martínez A. Casanova D. Alvarez S. Dalton Trans. 2008;19:2583–2591. doi: 10.1039/B718821H. PubMed DOI

Ho L. T. A. Chibotaru L. F. Phys. Rev. B. 2016;94:1–5.

Bartolomé J. FIloti G. Kuncser V. Schinteie G. Mereacre V. Anson C. E. Powell A. K. Prodius D. Turta C. Phys. Rev. B: Condens. Matter. 2009;80:014430. doi: 10.1103/PhysRevB.80.014430. DOI

Ishikawa R. Miyamoto R. Nojiri H. Breedlove B. K. Yamashita M. Inorg. Chem. 2013;52:8300–8302. doi: 10.1021/ic401351w. PubMed DOI

Nemec I. Marx R. Herchel R. Neugebauer P. van Slageren J. Travnicek Z. Dalton Trans. 2015;44:15014–15021. doi: 10.1039/C5DT02162F. PubMed DOI

Aquilante F. De Vico L. Ferré N. Ghigo G. Malmqvist P. Å. Neogrády P. Pedersen T. B. Pitoňák M. Reiher M. Roos B. O. Serrano-Andrés L. Urban M. Veryazov V. Lindh R. J. Comput. Chem. 2010;31:224–247. doi: 10.1002/jcc.21318. PubMed DOI

Duncan J. A. J. Am. Chem. Soc. 2009;131:2416. doi: 10.1021/ja900300h. PubMed DOI

Karlström G. Lindh R. Malmqvist P. Å. Roos B. O. Ryde U. Veryazov V. Widmark P.-O. Cossi M. Schimmelpfennig B. Neogrády P. Seijo L. Comput. Mater. Sci. 2003;28:222–239. doi: 10.1016/S0927-0256(03)00109-5. DOI

Veryazov V. Widmark P.-O. Serrano-Andres L. Lindh R. Roos B. O. Int. J. Quantum Chem. 2004;100:626–635. doi: 10.1002/qua.20166. DOI

Malmqvist P. Å. Roos B. O. Schimmelpfennig B. Chem. Phys. Lett. 2002;357:230–240. doi: 10.1016/S0009-2614(02)00498-0. DOI

Hess B. A. Marian C. M. Wahlgren U. Gropen O. Chem. Phys. Lett. 1996;251:365–371. doi: 10.1016/0009-2614(96)00119-4. DOI

Schimmelpfennig B., AMFI, an atomic mean-field spinorbit integral program, Stockholm University, 1996

Douglas N. Kroll N. M. Ann. Phys. 1974;82:89–155. doi: 10.1016/0003-4916(74)90333-9. DOI

Hess B. A. Phys. Rev. A. 1986;33:3742–3748. doi: 10.1103/PhysRevA.33.3742. PubMed DOI

Roos B. O. Lindh R. Malmqvist P. Å. Veryazov V. Widmark P.-O. J. Phys. Chem. A. 2008;112:11431–11435. doi: 10.1021/jp803213j. PubMed DOI

Roos B. O. Lindh R. Malmqvist P. Å. Veryazov V. Widmark P.-O. Chem. Phys. Lett. 2005;409:295–299. doi: 10.1016/j.cplett.2005.05.011. PubMed DOI

Chibotaru L. F. Ungur L. Soncini A. Angew. Chem., Int. Ed. 2008;47:4126–4129. doi: 10.1002/anie.200800283. PubMed DOI

Chibotaru L. F. Ungur L. Aronica C. Elmoll H. Pillet G. Luneau D. J. Am. Chem. Soc. 2008;130:12445–12455. doi: 10.1021/ja8029416. PubMed DOI

Chibotaru L. F. Ungur L. J. Chem. Phys. 2012;137:064112–064122. doi: 10.1063/1.4739763. PubMed DOI

Ungur L. Thewissen M. Costes J.-P. Wernsdorfer W. Chibotaru L. F. Inorg. Chem. 2013;52:6328–6337. doi: 10.1021/ic302568x. PubMed DOI

Momma K. Izumi F. J. Appl. Crystallogr. 2011;44:1272–127639. doi: 10.1107/S0021889811038970. DOI

Neese F. Wiley Interdiscip. Rev.: Comput. Mol. Sci. 2012;2:73–78.

Neese F. Wiley Interdiscip. Rev.: Comput. Mol. Sci. 2018;8:e1327.

Becke A. D. Phys. Rev. A: At., Mol., Opt. Phys. 1988;38:3098–3100. doi: 10.1103/PhysRevA.38.3098. PubMed DOI

Lee C. Yang W. Parr R. G. Phys. Rev. B: Condens. Matter Mater. Phys. 1988;37:785–789. doi: 10.1103/PhysRevB.37.785. PubMed DOI

Stephens P. J. Devlin F. J. Chabalowski C. F. Frisch M. J. J. Phys. Chem. 1994;98:11623–11627. doi: 10.1021/j100096a001. DOI

Weigend F. Ahlrichs R. Phys. Chem. Chem. Phys. 2005;7:3297–3305. doi: 10.1039/B508541A. PubMed DOI