{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,14]],"date-time":"2026-10-14T13:48:57Z","timestamp":1791985737917,"version":"4.4.0"},"reference-count":72,"publisher":"Wiley","issue":"1","license":[{"start":{"date-parts":[[2025,11,18]],"date-time":"2025-11-18T00:00:00Z","timestamp":1763424000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"},{"start":{"date-parts":[[2025,11,18]],"date-time":"2025-11-18T00:00:00Z","timestamp":1763424000000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["ChemPhysChem"],"published-print":{"date-parts":[[2026,1]]},"abstract":"<jats:p>\n                    A rigid H\u2010shaped [2]rotaxane shuttle composed by a mechanically interlocked 24\u2010crown\u20108(\n                    <jats:bold>24C8<\/jats:bold>\n                    ) macrocycle on a thread containing two symmetrical benzimidazole (Bzi) stations bound with a central 2,2\u2019\u2010bipyridyl (Bipy) core is addressed in CH\n                    <jats:sub>2<\/jats:sub>\n                    Cl\n                    <jats:sub>2<\/jats:sub>\n                    solution with all\u2010atoms molecular dynamics simulations. The experimentally observed conformational preferences of the\n                    <jats:bold>24C8<\/jats:bold>\n                    ring quantitatively characterizing the free\u2010energy landscape driving its reversible translocation over the synthetic Stop\u2010[Bzi\u2010Bipy\u2010Bzi]\u2010Stop thread at room temperature have been reproduced. Also, this analysis to a translationally inactive form in N,N\u2010dimethylformamide (DMF) dilute solution following the coordination of PtCl\n                    <jats:sub>2<\/jats:sub>\n                    to the Bipy chelate site is extended. In this respect, in the presence of PtCl\n                    <jats:sub>2<\/jats:sub>\n                    , the optimized geometry within the density functional theory (DFT) framework is fully characterized in terms of quantum theory of atoms in molecules (QTAIM) descriptors. Converged DFT wavefunctions in a continuum environment are analytically investigated by means of electron density\n                    <jats:italic>\n                      \u03c1(\n                      <jats:bold>r<\/jats:bold>\n                      )\n                    <\/jats:italic>\n                    , local electronic energy density,\n                    <jats:italic>\n                      H(\n                      <jats:bold>r<\/jats:bold>\n                      ),\n                    <\/jats:italic>\n                    electron localization function (ELF), and delocalization index \u03b4(X,Y) analysis. The derived picture highlights that the contextual presence of supramolecular contacts confining the\n                    <jats:bold>24C8<\/jats:bold>\n                    ring over its primary recognition site, and of a planar square (Bipy)\u2010N\n                    <jats:sub>2<\/jats:sub>\n                    \u2010Pt\n                    <jats:sup>(II)<\/jats:sup>\n                    Cl\n                    <jats:sub>2<\/jats:sub>\n                    coordination environment parallel to the axle should actually be effective in suppressing the shutting movement as hypothesized via\n                    <jats:sup>1<\/jats:sup>\n                    H\u2010nuclear magnetic resonance measurements.\n                  <\/jats:p>","DOI":"10.1002\/cphc.202500660","type":"journal-article","created":{"date-parts":[[2025,11,18]],"date-time":"2025-11-18T18:14:40Z","timestamp":1763489680000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["A Computational Study of a [2]Rotaxane Molecular Shuttle with All\u2010Atoms Molecular Dynamics and Density Functional Theory Simulations in Solution"],"prefix":"10.1002","volume":"27","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-9050-1874","authenticated-orcid":false,"given":"Costantino","family":"Zazza","sequence":"first","affiliation":[{"name":"Department for Innovation in Biological, Agro\u2010food and Forest systems Universit\u00e0 della Tuscia (DIBAF)  L.go dell\u2019Universit\u00e0, s.n.c. 01100 Viterbo Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1947-7939","authenticated-orcid":false,"given":"Nico","family":"Sanna","sequence":"additional","affiliation":[{"name":"Department for Innovation in Biological, Agro\u2010food and Forest systems Universit\u00e0 della Tuscia (DIBAF)  L.go dell\u2019Universit\u00e0, s.n.c. 01100 Viterbo Italy"},{"name":"CNR\u2010ISTP (Istituto per la Scienza e Tecnologia dei Plasmi)  Via G. Amendola 122\/D 70126 Bari Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4931-3019","authenticated-orcid":false,"given":"Stefano","family":"Borocci","sequence":"additional","affiliation":[{"name":"Department for Innovation in Biological, Agro\u2010food and Forest systems Universit\u00e0 della Tuscia (DIBAF)  L.go dell\u2019Universit\u00e0, s.n.c. 01100 Viterbo Italy"},{"name":"Istituto per i Sistemi Biologici del CNR (ISB) Sede di Roma\u2013Meccanismi di Reazione c\/o Dipartimento di Chimica Sapienza Universit\u00e0 di Roma  P.le A. Moro 5 001855 Rome Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7217-9490","authenticated-orcid":false,"given":"Felice","family":"Grandinetti","sequence":"additional","affiliation":[{"name":"Department for Innovation in Biological, Agro\u2010food and Forest systems Universit\u00e0 della Tuscia (DIBAF)  L.go dell\u2019Universit\u00e0, s.n.c. 01100 Viterbo Italy"},{"name":"Istituto per i Sistemi Biologici del CNR (ISB) Sede di Roma\u2013Meccanismi di Reazione c\/o Dipartimento di Chimica Sapienza Universit\u00e0 di Roma  P.le A. Moro 5 001855 Rome Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2025,11,18]]},"reference":[{"key":"e_1_2_9_2_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201703216"},{"key":"e_1_2_9_3_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201702992"},{"key":"e_1_2_9_4_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201702979"},{"key":"e_1_2_9_5_1","doi-asserted-by":"publisher","DOI":"10.1002\/3527607439"},{"key":"e_1_2_9_6_1","doi-asserted-by":"publisher","DOI":"10.1002\/9783527621682"},{"key":"e_1_2_9_7_1","volume-title":"Nanotechnology and Life","author":"Jones R. A. L.","year":"2004"},{"key":"e_1_2_9_8_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(00)94050-4"},{"key":"e_1_2_9_9_1","doi-asserted-by":"publisher","DOI":"10.1039\/b500680p"},{"key":"e_1_2_9_10_1","doi-asserted-by":"publisher","DOI":"10.1039\/B605172N"},{"key":"e_1_2_9_11_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00998a052"},{"key":"e_1_2_9_12_1","doi-asserted-by":"publisher","DOI":"10.1039\/D4CS00430B"},{"key":"e_1_2_9_13_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202304025"},{"key":"e_1_2_9_14_1","doi-asserted-by":"publisher","DOI":"10.1038\/s42004-024-01205-3"},{"key":"e_1_2_9_15_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.1057886"},{"key":"e_1_2_9_16_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja0352552"},{"key":"e_1_2_9_17_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.cplett.2023.140758"},{"key":"e_1_2_9_18_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.comptc.2012.01.039"},{"key":"e_1_2_9_19_1","doi-asserted-by":"publisher","DOI":"10.1039\/C8CC08681H"},{"key":"e_1_2_9_20_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.8b01019"},{"key":"e_1_2_9_21_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202302114"},{"key":"e_1_2_9_22_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202300633"},{"key":"e_1_2_9_23_1","doi-asserted-by":"publisher","DOI":"10.1038\/nnano.2014.260"},{"key":"e_1_2_9_24_1","doi-asserted-by":"publisher","DOI":"10.1021\/jz4019404"},{"key":"e_1_2_9_25_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscentsci.0c00064"},{"key":"e_1_2_9_26_1","doi-asserted-by":"publisher","DOI":"10.1002\/open.202500229"},{"key":"e_1_2_9_27_1","doi-asserted-by":"publisher","DOI":"10.1039\/D3SC01346D"},{"key":"e_1_2_9_28_1","doi-asserted-by":"publisher","DOI":"10.1039\/C7SC03736H"},{"key":"e_1_2_9_29_1","doi-asserted-by":"publisher","DOI":"10.1002\/cphc.202500074"},{"key":"e_1_2_9_30_1","doi-asserted-by":"publisher","DOI":"10.1063\/5.0045455"},{"key":"e_1_2_9_31_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr00005a013"},{"key":"e_1_2_9_32_1","volume-title":"Atoms In Molecules: A Quantum Theory","author":"Bader R. 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J.Frisch G. W.Trucks H. B.Schlegel G. E.Scuseria M. A.Robb J. R.Cheeseman G.Scalmani V.Barone G. A.Petersson H.Nakatsuji X.Li M.Caricato A. V.Marenich J.Bloino B. G.Janesko R.Gomperts B.Mennucci H. P.Hratchian J. V.Ortiz A. F.Izmaylov J. L.Sonnenberg D.Williams\u2010Young F.Ding F.Lipparini F.Egidi J.Goings B.Peng A.Petrone T.Henderson D. J.Fox et al.Gaussian Inc. Wallingford CT2016."},{"key":"e_1_2_9_50_1","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1096-987X(199709)18:12<1463::AID-JCC4>3.0.CO;2-H"},{"key":"e_1_2_9_51_1","doi-asserted-by":"publisher","DOI":"10.1021\/ct200731v"},{"key":"e_1_2_9_52_1","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.20291"},{"key":"e_1_2_9_53_1","unstructured":"A harmonic restraint potential of 30 kJ mol\u22121\u00c5\u22122was applied to confine such a coordinate within a region of \u22488 \u00c5 and composed of 16 evenly spaced intervals. For each interval a 20 ns MD simulation (T\u2009=\u2009298 K;p\u2009=\u20091 bar) was carried out for a total time of 320 ns. The first 200 ps was disregarded in the derivation of the Potential of Mean Force (PMF); forces and mutual displacements were stored every 2 ps."},{"key":"e_1_2_9_54_1","doi-asserted-by":"publisher","DOI":"10.1021\/ct100494z"},{"key":"e_1_2_9_55_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.5010587"},{"key":"e_1_2_9_56_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.comptc.2014.10.011"},{"key":"e_1_2_9_57_1","doi-asserted-by":"publisher","DOI":"10.1063\/5.0216272"},{"key":"e_1_2_9_58_1","doi-asserted-by":"publisher","DOI":"10.1039\/C7CP02110K"},{"key":"e_1_2_9_59_1","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.26812"},{"key":"e_1_2_9_60_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202504895"},{"key":"e_1_2_9_61_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.458517"},{"key":"e_1_2_9_62_1","doi-asserted-by":"publisher","DOI":"10.1038\/371683a0"},{"key":"e_1_2_9_63_1","unstructured":"A \u201ccritical point\u201d (CP rcp) in the\u03c1(r) electron density is a particular point in space in which the first derivatives of the density vanish (i.e. \u2207\u03c1(r)\u2009=\u20090 where each individual derivative in the gradient operator \u2207 is zero and not just their sum). The rank of a CP is equal to the number of non\u2010zero eigenvalues of the symmetric matrix known as the Hessian of\u03c1(rcp) [non\u2010zero curvatures of\u03c1(rcp) at the CPs] and signature is the algebraic sum of the signs of eigenvalues. There are then four possible values for CPs of rank three. They are (3 \u22123) (3 \u22121) (3 +1) and (3 +3). In the case of (3 \u22123) all curvatures are negative and\u03c1is a local maximum atrcp. For (3 \u22121) the two curvatures are negative and \u03c1 is a maximum atrcplying in the plane defined by their local corresponding axes. Further \u03c1is a minimum at CP along the third axis which is perpendicular to this plane. The (3 +1) CP has two positive curvatures and\u03c1is a minimum at CP in the plane defined by their corresponding axes. Further \u03c1is a maximum at CP along the third axis which is perpendicular to this plane. The (3 +3) CP represents all curvatures are positive and\u03c1is a local minimum atrcp(cage critical points CCPs). The topological distribution of the\u03c1(r) is able to characterize the nuclear positions featuring rcp of kind (3 \u22123) since the nuclei act as the attractors of the gradient of \u03c1 distribution of molecules. The presence of a (3 \u22121) CP and related atomic interaction line highlights that electronic charge density is accumulated between the nuclei that are linked by a chemical bond. The (3 +1) CP are typically found in the interior of the ring and are known as ring critical points (RCPs)."},{"key":"e_1_2_9_64_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp906341r"},{"key":"e_1_2_9_65_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp983362q"},{"key":"e_1_2_9_66_1","doi-asserted-by":"publisher","DOI":"10.1007\/s00214-002-0356-8"},{"key":"e_1_2_9_67_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp0538464"},{"key":"e_1_2_9_68_1","unstructured":"Studying the nature of the chemical bond in many explored species at quantum mechanics level we recently proposed (see Ref. 37) the following general classification: (a) a bond is assigned as covalent (Cov) if\u03b4(X Y) \u2265 0.8e irrespective of\u03c1(rcp); (b) a bond is assigned as polar covalent [Cov(pol)] or partially covalent (pCov) if 0.2e< \u03b4(X Y) < 0.8e and if\u03c1(rcp) \u2265 0.05e\u00b7a0\u22123 or\u03c1(rcp) < 0.05e\u00b7a0\u22123 respectively; (c) a bond is assigned as weakly covalent (wCov) if\u03b4(X Y) < 0.2e irrespective of the associated\u03c1(rcp)."},{"key":"e_1_2_9_69_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja01489a006"},{"key":"e_1_2_9_70_1","unstructured":"The 3D plot of theH(0 ISO)isosurface reported in the additional material also unequivocally shows the presence of a covalent network connecting the PtCl2 moiety to the functionalized Stop\u2010[Bzi\u2010Bipy\u2010Bzi]\u2010Stop molecular thread.[37]"},{"key":"e_1_2_9_71_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.4918025"},{"key":"e_1_2_9_72_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.cplett.2004.12.096"},{"key":"e_1_2_9_73_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsomega.8b03455"}],"container-title":["ChemPhysChem"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/cphc.202500660","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/cphc.202500660","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/cphc.202500660","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,1,16]],"date-time":"2026-01-16T17:00:25Z","timestamp":1768582825000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/cphc.202500660"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2025,11,18]]},"references-count":72,"journal-issue":{"issue":"1","published-print":{"date-parts":[[2026,1]]}},"alternative-id":["10.1002\/cphc.202500660"],"URL":"https:\/\/doi.org\/10.1002\/cphc.202500660","archive":["Portico"],"relation":{},"ISSN":["1439-4235","1439-7641"],"issn-type":[{"value":"1439-4235","type":"print"},{"value":"1439-7641","type":"electronic"}],"subject":[],"published":{"date-parts":[[2025,11,18]]},"assertion":[{"value":"2025-09-10","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2025-11-18","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202500660"}}