Theoretical and Experimental Study of New Photochromic Bis-Spiropyrans with Hydroxyethyl and Carboxyethyl Substituents

<table>UV absorption spectrum of a bis-spiropyran (<b>2b</b>) in acetonitrile solution before and after continuous irradiation with <svg height="16.450001" id="M37" style="vertical-align:-3.39066pt" version="1.1" viewbox="0 0 76.599998 16.450001" width="76.599998" xmlns="http://www.w3.org/2000/svg" xmlns:xlink="http://www.w3.org/1999/xlink">
<g transform="matrix(.017,-0,0,-.017,.062,12.162)"><path d="M529 97q-70 -109 -136 -109q-41 0 -56 94q-23 144 -37 284q-38 -88 -99 -202.5t-93 -156.5q-26 -8 -76 -19l-9 21q71 78 145.5 193t124.5 232q-5 84 -15 128q-12 55 -29.5 75.5t-42.5 20.5q-21 0 -45 -13l-8 24q16 17 46 30t55 13q43 0 70 -46.5t40 -169.5
q27 -249 51 -392q7 -46 23 -46q24 0 70 60z" id="x1D706"></path></g>
<g transform="matrix(.012,-0,0,-.012,9.45,16.25)"><path d="M797 0h-214v26q46 5 58 17.5t12 63.5v167q0 116 -88 116q-48 0 -112 -52q3 -18 3 -42v-195q0 -46 11 -58t53 -17v-26h-214v26q48 5 59.5 17t11.5 60v172q0 115 -88 115q-47 0 -109 -52v-235q0 -47 10 -59.5t48 -17.5v-26h-211v26q50 5 62.5 17t12.5 60v207q0 48 -9 59.5
t-52 18.5v23q79 14 139 41v-81q3 2 29 20.5t44 29.5q45 28 81 28t66 -22t46 -61q25 20 83 57q39 26 76 26q59 0 93 -40t34 -113v-193q0 -49 10.5 -60.5t54.5 -16.5v-26z" id="x6D"></path></g><g transform="matrix(.012,-0,0,-.012,19.195,16.25)"><path d="M433 39l-85 -51q-27 0 -47 20q-16 16 -24 44q-5 -3 -24 -16.5t-27 -18.5t-23 -13.5t-25 -12t-19 -3.5q-52 0 -86 36.5t-34 85.5q0 71 81 99q128 43 155 65v17q0 54 -23 83.5t-62 29.5q-28 0 -45 -19t-29 -66q-7 -23 -29 -23q-15 0 -29 13t-14 30t31 40q25 19 68.5 40.5
t81.5 29.5q49 0 82 -27q45 -39 45 -123v-185q0 -60 35 -60q18 0 36 11zM275 84v156q-12 -6 -49 -23t-41 -19q-31 -14 -46 -31t-15 -43q0 -35 22.5 -55.5t48.5 -20.5q19 0 42 10.5t38 25.5z" id="x61"></path></g><g transform="matrix(.012,-0,0,-.012,24.419,16.25)"><path d="M474 0h-214v26q32 4 39 12t-5 28l-74 117q-39 -58 -64 -106q-16 -25 -10 -35t44 -16v-26h-186v26q46 6 64 17t48 49t85 120l-87 136q-23 36 -40 47t-58 16v26h199v-26q-31 -4 -36.5 -12.5t9.5 -29.5l59 -93q37 56 58 94q13 23 7 30t-40 11v26h183v-26q-47 -5 -65 -13.5
t-45 -39.5q-24 -29 -78 -110l97 -148q28 -43 46.5 -55.5t63.5 -18.5v-26z" id="x78"></path></g>
<g transform="matrix(.017,-0,0,-.017,37.362,12.162)"><path d="M535 323h-483v50h483v-50zM535 138h-483v50h483v-50z" id="x3D"></path></g><g transform="matrix(.017,-0,0,-.017,52.049,12.162)"><path d="M285 378v-2q65 -13 102 -54.5t37 -97.5q0 -57 -30.5 -104.5t-74 -75t-85.5 -42t-72 -14.5q-31 0 -59.5 11t-40.5 23q-19 18 -16 36q1 16 23 33q13 10 24 0q58 -51 124 -51q55 0 88 40t33 112q0 64 -39 96.5t-88 32.5q-29 0 -64 -11l-6 29q77 25 118 57.5t41 84.5
q0 45 -26.5 69.5t-68.5 24.5q-67 0 -120 -79l-20 20l43 63q51 56 127 56h1q66 0 107 -37t41 -95q0 -42 -31 -71q-22 -23 -68 -54z" id="x33"></path></g><g transform="matrix(.017,-0,0,-.017,60.209,12.162)"><path d="M137 343l67 33q37 17 63 17q79 0 129.5 -53t50.5 -131q0 -92 -58 -156.5t-147 -64.5t-147 68t-58 182q0 63 17 119t43 95.5t61.5 72t69 52t67.5 31.5q62 22 128 33l6 -32q-56 -11 -108 -35q-149 -71 -184 -231zM227 337q-47 0 -95 -27q-6 -23 -6 -70q0 -93 36 -155.5
t96 -62.5q53 0 78 45.5t25 105.5q0 68 -35 116t-99 48z" id="x36"></path></g><g transform="matrix(.017,-0,0,-.017,68.368,12.162)"><path d="M153 550l-26 -186q79 31 111 31q90 0 141.5 -51t51.5 -119q0 -93 -89 -166q-85 -69 -173 -71q-32 0 -61.5 11.5t-41.5 23.5q-18 17 -17 34q2 16 22 33q14 9 26 -1q61 -50 124 -50q60 0 93 43.5t33 104.5q0 69 -41.5 110t-121.5 41q-53 0 -102 -20l38 305h286l6 -8
l-26 -65h-233z" id="x35"></path></g>
</svg> nm (<svg height="18.575001" id="M38" style="vertical-align:-2.22495pt" version="1.1" viewbox="0 0 107.8875 18.575001" width="107.8875" xmlns="http://www.w3.org/2000/svg" xmlns:xlink="http://www.w3.org/1999/xlink">
<g transform="matrix(.017,-0,0,-.017,.062,15.738)"><path d="M290 -163h-170v866h170v-28q-79 -7 -94 -19.5t-15 -72.5v-627q0 -59 14.5 -71.5t94.5 -19.5v-28z" id="x5B"></path></g><g transform="matrix(.017,-0,0,-.017,5.927,15.738)"><path d="M390 111l17 -21q-34 -45 -80 -73.5t-89 -28.5q-91 0 -146 62t-55 147q0 118 101 195q74 57 149 57h1q59 0 90 -27q16 -14 16 -30q0 -15 -12 -29t-21 -14q-8 0 -19 11q-44 41 -101 41q-52 0 -87.5 -42.5t-35.5 -117.5q0 -49 15 -87t39 -58t49 -30t48 -10q33 0 60.5 12
t60.5 43z" id="x63"></path></g><g transform="matrix(.017,-0,0,-.017,13.118,15.738)"><path d="M226 -163h-170v27q79 7 94 20t15 73v627q0 59 -15 72t-94 20v27h170v-866z" id="x5D"></path></g><g transform="matrix(.017,-0,0,-.017,23.691,15.738)"><path d="M535 323h-483v50h483v-50zM535 138h-483v50h483v-50z" id="x3D"></path></g><g transform="matrix(.017,-0,0,-.017,38.395,15.738)"><path d="M384 0h-275v27q67 5 81.5 18.5t14.5 68.5v385q0 38 -7.5 47.5t-40.5 10.5l-48 2v24q85 15 178 52v-521q0 -55 14.5 -68.5t82.5 -18.5v-27z" id="x31"></path></g><g transform="matrix(.017,-0,0,-.017,46.554,15.738)"><path d="M113 -12q-24 0 -39.5 16t-15.5 42q0 24 16 40.5t40 16.5t40 -16.5t16 -40.5q0 -26 -16 -42t-41 -16z" id="x2E"></path></g><g transform="matrix(.017,-0,0,-.017,50.43,15.738)"><path d="M249 635q70 0 116 -43t46 -105q0 -46 -28 -80q-22 -25 -80 -64q62 -35 97 -75t35 -99q0 -81 -63 -131t-135 -50q-83 0 -137.5 45.5t-54.5 123.5q0 52 45 95q29 28 89 64q-109 62 -109 155q0 66 50.5 115t128.5 49zM238 603q-42 0 -67.5 -31t-25.5 -72q0 -50 32.5 -79.5
t98.5 -62.5q61 48 61 124q0 59 -29.5 90t-69.5 31zM248 20q46 0 76.5 33.5t30.5 89.5q0 50 -39 85.5t-110 71.5q-81 -54 -81 -137q0 -67 35.5 -105t87.5 -38z" id="x38"></path></g><g transform="matrix(.017,-0,0,-.017,58.589,15.738)"><path d="M137 343l67 33q37 17 63 17q79 0 129.5 -53t50.5 -131q0 -92 -58 -156.5t-147 -64.5t-147 68t-58 182q0 63 17 119t43 95.5t61.5 72t69 52t67.5 31.5q62 22 128 33l6 -32q-56 -11 -108 -35q-149 -71 -184 -231zM227 337q-47 0 -95 -27q-6 -23 -6 -70q0 -93 36 -155.5
t96 -62.5q53 0 78 45.5t25 105.5q0 68 -35 116t-99 48z" id="x36"></path></g><g transform="matrix(.017,-0,0,-.017,70.522,15.738)"><path d="M170 255q0 -25 -16 -41t-40 -16t-40 16t-16 41t16 41.5t40 16.5t40 -16.5t16 -41.5z" id="x22C5"></path></g><g transform="matrix(.017,-0,0,-.017,78.172,15.738)"><path d="M384 0h-275v27q67 5 81.5 18.5t14.5 68.5v385q0 38 -7.5 47.5t-40.5 10.5l-48 2v24q85 15 178 52v-521q0 -55 14.5 -68.5t82.5 -18.5v-27z" id="x31"></path></g><g transform="matrix(.017,-0,0,-.017,86.331,15.738)"><path d="M241 635q53 0 94 -28.5t63.5 -76t33.5 -102.5t11 -116q0 -58 -11 -112.5t-34 -103.5t-63.5 -78.5t-94.5 -29.5t-95 28t-64.5 75t-34.5 102.5t-11 118.5q0 58 11.5 112.5t34.5 103t64.5 78t95.5 29.5zM238 602q-32 0 -55.5 -25t-35.5 -68t-17.5 -91t-5.5 -105
q0 -76 10 -138.5t37 -107.5t69 -45q32 0 55.5 25t35.5 68.5t17.5 91.5t5.5 105t-5.5 105.5t-18 92t-36 68t-56.5 24.5z" id="x30"></path></g>
<g transform="matrix(.012,-0,0,-.012,94.512,7.587)"><path d="M535 230h-483v50h483v-50z" id="x2212"></path></g><g transform="matrix(.012,-0,0,-.012,101.497,7.587)"><path d="M456 178h-96v-72q0 -51 12.5 -62.5t72.5 -16.5v-27h-256v27q65 5 78 17t13 62v72h-260v28q182 271 300 426h40v-407h96v-47zM280 225v295h-2q-107 -148 -196 -295h198z" id="x34"></path></g>
</svg> M; <svg height="11.875" id="M39" style="vertical-align:-0.20474pt" version="1.1" viewbox="0 0 55.349998 11.875" width="55.349998" xmlns="http://www.w3.org/2000/svg" xmlns:xlink="http://www.w3.org/1999/xlink">
<g transform="matrix(.017,-0,0,-.017,.062,11.55)"><path d="M649 676l-22 -187l-33 -2q3 56 -12 94q-8 20 -31.5 26.5t-86.5 6.5h-74l-90 -491q-4 -23 -6 -36.5t1 -25t7 -16.5t18 -9t27 -5t41 -3l-6 -28h-286l4 28q68 5 84 18.5t28 76.5l94 491h-55q-74 0 -100.5 -6t-41.5 -23q-24 -29 -54 -98l-32 1q32 98 53 188h22q7 -18 15 -22
t37 -4h417q23 0 33.5 5t25.5 21h23z" id="x1D447"></path></g><g transform="matrix(.017,-0,0,-.017,16.092,11.55)"><path d="M535 323h-483v50h483v-50zM535 138h-483v50h483v-50z" id="x3D"></path></g><g transform="matrix(.017,-0,0,-.017,30.796,11.55)"><path d="M412 140l28 -9q0 -2 -35 -131h-373v23q112 112 161 170q59 70 92 127t33 115q0 63 -31 98t-86 35q-75 0 -137 -93l-22 20l57 81q55 59 135 59q69 0 118.5 -46.5t49.5 -122.5q0 -62 -29.5 -114t-102.5 -130l-141 -149h186q42 0 58.5 10.5t38.5 56.5z" id="x32"></path></g><g transform="matrix(.017,-0,0,-.017,38.956,11.55)"><path d="M244 635q90 0 143 -72t53 -177q0 -133 -65 -229.5t-171 -139.5q-79 -32 -140 -32l-5 30q109 18 185 91t101 186l-68 -36q-29 -16 -60 -16q-79 0 -129 51.5t-50 130.5q0 80 57 146.5t149 66.5zM228 602q-52 0 -78 -45.5t-26 -98.5q0 -69 36.5 -115.5t97.5 -46.5
q53 0 90 28q4 31 4 66q0 51 -9.5 95.5t-39 80.5t-75.5 36z" id="x39"></path></g><g transform="matrix(.017,-0,0,-.017,47.115,11.55)"><path d="M285 378v-2q65 -13 102 -54.5t37 -97.5q0 -57 -30.5 -104.5t-74 -75t-85.5 -42t-72 -14.5q-31 0 -59.5 11t-40.5 23q-19 18 -16 36q1 16 23 33q13 10 24 0q58 -51 124 -51q55 0 88 40t33 112q0 64 -39 96.5t-88 32.5q-29 0 -64 -11l-6 29q77 25 118 57.5t41 84.5
q0 45 -26.5 69.5t-68.5 24.5q-67 0 -120 -79l-20 20l43 63q51 56 127 56h1q66 0 107 -37t41 -95q0 -42 -31 -71q-22 -23 -68 -54z" id="x33"></path></g>
</svg>°K; curves are recorded with 15 s interval).</table>

International Journal of Photoenergy

fig10

Figure 10

Figure 10: Theoretical and Experimental Study of New Photochromic Bis-Spiropyrans with Hydroxyethyl and Carboxyethyl Substituents 