{"id":13300,"date":"2015-02-04T18:48:46","date_gmt":"2015-02-04T18:48:46","guid":{"rendered":"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/?p=13300"},"modified":"2015-02-09T13:12:01","modified_gmt":"2015-02-09T13:12:01","slug":"mechanism-of-the-solvatochromic-reaction-of-a-spiropyran","status":"publish","type":"post","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=13300","title":{"rendered":"Mechanism of the solvatochromic reaction of a spiropyran."},"content":{"rendered":"
\n

The journal of chemical education has many little gems providing inspiration for laboratory experiments. Jonathan Piard reports one based on the reaction below[1]<\/a><\/span>; here I investigate the mechanism of this transformation.<\/p>\n

\"spiropyran\"<\/a>
\nThere are two things going on here; an electrocyclic ring opening involving breaking the C-O bond, with\u00a0a cis\/trans<\/em> isomerism of the alkene (concurrent or consecutive). A crystal structure of the dinitro analogue establishes the trans<\/em> stereochemistry[2]<\/a><\/span>. This product zwitterion is highly coloured (blue-purple) unlike the colourless reactant. The rate at which this colour clears can be easily measured in a UV\/visible spectrometer, and from this activation parameters are inferred\u00a0as a function of the solvent.<\/p>\n

Photochemically, this reaction is too complex to study quickly using computation, but the thermal back reaction is much easier. Applying the \u03c9B97XD\/6-311G(d,p)\/SCRF=solvent procedure and using the C-O bond as a reaction coordinate results in the following transition state[3]<\/a><\/span> IRC profile[4]<\/a><\/span> for DMSO as solvent,\u00a0here connecting to the\u00a0cis<\/em>-alkene.\u00a0The thermal forward barrier for the C…O cleaving\u00a0is ~12 kcal\/mol. More significantly, the back reaction is only <2 kcal mol, which is very much lower than that reported[1]<\/a><\/span> (~22 kcal\/mol) and makes the cis<\/em>-alkene very much a transient species\u00a0and therefore not<\/strong> the\u00a0coloured species being measured.<\/p>\n

\"C-O-cleave\"<\/a><\/p>\n

A second transition state involving C=C bond rotation is located[5]<\/a><\/span> and this yields the following IRC[6]<\/a><\/span> to form the trans<\/em>-alkene, with activation parameters listed below.\u00a0It is entirely probable however that the forward photochemical reaction follows a different course involving conical intersections; an interesting study in its own right, but beyond the scope of this post.<\/p>\n

\"cis-trans\"<\/a><\/p>\n\n\n\n\n\n\n\n\n
Measured and computed activation parameters for the thermal back\u00a0reaction<\/th>\n<\/tr>\n
Solvent<\/th>\n\u0394G298<\/sub>, kcal mol-1<\/sup><\/th>\n\u0394H, kcal mol-1<\/sup><\/th>\n\u0394S, cal K-1<\/sup> mol-1<\/sup><\/th>\n<\/tr>\n
DMSO, measured<\/td>\n22.0<\/td>\n26.4<\/span><\/td>\n+14.6<\/span><\/td>\n<\/tr>\n
toluene, measured<\/td>\n19.0<\/td>\n14.3<\/span><\/td>\n-15.6<\/span><\/td>\n<\/tr>\n
DMSO, calc[5]<\/a><\/span><\/td>\n21.2<\/td>\n20.4<\/td>\n+2.6<\/td>\n<\/tr>\n
toluene, calc[7]<\/a><\/span><\/td>\n18.6<\/td>\n19.1<\/td>\n+1.8<\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n

The next issue surrounds the effect of solvent. Most spectacular are those of the\u00a0activation parameters for the thermal back-reaction. The measured activation entropy \u0394S changes with solvent by \u039430.2<\/strong><\/span> cal, and the enthalpy \u0394H by \u039412.1<\/strong><\/span> kcal, which are enormous solvent effects. Are they in fact real? It is reassuring at least that the calculated free energy agrees pretty closely with the measured values. So too does the decrease in\u00a0\u0394G in changing the solvent from DMSO to toluene (3.0 kcal\/mol measured, 2.6 calculated).<\/p>\n

There is little sign of a large solvent effect in the calculated values. This could be for three reasons.<\/p>\n

    \n
  1. The first is that adding explicit, hydrogen-bonded solvent molecules to the system is essential. As the zwitterionic character is lost when the trans<\/em>-alkene starts to rotate, the system will become less ionic, and hence shed solvent molecules and gain entropy. If the solvent is not capable of hydrogen bonding, as say toluene, these will not be shed and the entropy will not increase at the transition state. It is difficult however to reconcile this picture with the apparent large loss of entropy for toluene as solvent.<\/li>\n
  2. The second reason is because of a complete change in mechanism, one not modelled here.<\/li>\n
  3. For completeness, one should also mention that the measured values might simply be in error, either due to typographical mistakes or indeed in numerical analysis.<\/li>\n<\/ol>\n

    I will conclude with the colour.\u00a0It is possible to compute the electronic excitations across the range 180-580nm, and I show below a difference spectrum<\/em> (for DMSO as solvent) with the product +ve and the reactant \u00a0-ve. You can see the spectacular red-shift for the highly conjugated zwitterion! The absolute value of \u03bbmax<\/sub> is not red-shifted enough (by about 65 nm), but the effect remains real.
    \n\"spiro\"<\/a><\/p>\n

    The above experiment is for undergraduate chemistry laboratories. I suggest that a computational reality check could also easily be included into such a lab, and would certainly help give students a broader perspective.<\/p>\n

    References<\/h2>\n
    1. J. Piard, \"Influence of the Solvent on the Thermal Back Reaction of One Spiropyran\", Journal of Chemical Education<\/i>, vol. 91, pp. 2105-2111, 2014. https:\/\/doi.org\/10.1021\/ed4005003<\/a>\n\n<\/li>\n
    2. J. Hobley, V. Malatesta, R. Millini, L. Montanari, and W. O Neil Parker, Jr, \"Proton exchange and isomerisation reactions of photochromic and reverse photochromic spiro-pyrans and their merocyanine forms\", Physical Chemistry Chemical Physics<\/i>, vol. 1, pp. 3259-3267, 1999. https:\/\/doi.org\/10.1039\/a902379h<\/a>\n\n<\/li>\n
    3. H.S. Rzepa, \"C 19 H 18 N 2 O 3\", 2015. https:\/\/doi.org\/10.14469\/ch\/189540<\/a>\n\n<\/li>\n
    4. H.S. Rzepa, \"C19H18N2O3\", 2015. https:\/\/doi.org\/10.14469\/ch\/189573<\/a>\n\n<\/li>\n
    5. H.S. Rzepa, \"C 19 H 18 N 2 O 3\", 2015. https:\/\/doi.org\/10.14469\/ch\/189546<\/a>\n\n<\/li>\n
    6. H.S. Rzepa, \"C19H18N2O3\", 2015. https:\/\/doi.org\/10.14469\/ch\/189648<\/a>\n\n<\/li>\n
    7. H.S. Rzepa, \"C 19 H 18 N 2 O 3\", 2015. https:\/\/doi.org\/10.14469\/ch\/189579<\/a>\n\n<\/li>\n<\/ol>\n\n<\/div> ","protected":false},"excerpt":{"rendered":"

      The journal of chemical education has many little gems providing inspiration for laboratory experiments. Jonathan Piard reports one based on the reaction below; here I investigate the mechanism of this transformation. There are two things going on here; an electrocyclic ring opening involving breaking the C-O bond, with\u00a0a cis\/trans isomerism of the alkene (concurrent or […]<\/p>\n","protected":false},"author":1,"featured_media":0,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"jetpack_post_was_ever_published":false,"_jetpack_newsletter_access":"","_jetpack_dont_email_post_to_subs":false,"_jetpack_newsletter_tier_id":0,"_jetpack_memberships_contains_paywalled_content":false,"_jetpack_memberships_contains_paid_content":false,"activitypub_content_warning":"","activitypub_content_visibility":"","activitypub_max_image_attachments":5,"activitypub_interaction_policy_quote":"anyone","activitypub_status":"","footnotes":"","jetpack_publicize_message":"","jetpack_publicize_feature_enabled":true,"jetpack_social_post_already_shared":true,"jetpack_social_options":{"image_generator_settings":{"template":"highway","default_image_id":0,"font":"","enabled":false},"version":2}},"categories":[1086],"tags":[466,1202,1316],"ppma_author":[2661],"class_list":["post-13300","post","type-post","status-publish","format-standard","hentry","category-reaction-mechanism-2","tag-calculated-free-energy","tag-chemical-education","tag-jonathan-piard"],"yoast_head":"\nMechanism of the solvatochromic reaction of a spiropyran. - Henry Rzepa's Blog<\/title>\n<meta name=\"robots\" content=\"index, follow, max-snippet:-1, max-image-preview:large, max-video-preview:-1\" \/>\n<link rel=\"canonical\" href=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=13300\" \/>\n<meta property=\"og:locale\" content=\"en_GB\" \/>\n<meta property=\"og:type\" content=\"article\" \/>\n<meta property=\"og:title\" content=\"Mechanism of the solvatochromic reaction of a spiropyran. - Henry Rzepa's Blog\" \/>\n<meta property=\"og:description\" content=\"The journal of chemical education has many little gems providing inspiration for laboratory experiments. Jonathan Piard reports one based on the reaction below; here I investigate the mechanism of this transformation. 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