further reserhD yet this demonstrtes the lrge sope for vrition o'ered y stndrd syntheti reipeF rile wter ontent is likely prtil use of the di'erene in resultsF he kineti e'ets of wter on the formtion of gxEPPRGdgxEPPR were reently highlightedF 27 rgl 4 is hygrosopiY thus pristine rgl 4 results in n intermediteD wheres rgl 4 exposed to ir yields either gxEPPP or gxEPPR depending on the exposure timeF 27 hile nedotlD it is worth noting tht hP nd hRD whih were synthesised from nhydrous rD did not yield ny known r!porphyrin wyp nd morphised upon tivtionF he importne of wter is lso known for other wyp synthesesF 4649 sn ddition to the wter in the r IV soureD mient humidity nd the wter ontent of the solvent will vryF he prtiipnts in this study spn limtes rnging from desert to humid sutropilD 50,51 whih my hve n e'et"lthough mny modern ls re irEonditionedF vikewiseD the freshness of the solvent is ritilD s mideEsed solvents re prone to hydrolysisF epeting the interlortory study with wter s ontrolled vrile would provide n estimte of the extent to whih wter dittes the syntheti outomeF fesides wterD other ftors my lso ontriute to the vrition in resultsF he retions involve signi(nt uildEup of pressureD ditted y the volume nd hedspe of the reE tion vesselD whih were not ontrolled in our studyF yur experienes indite tht hnging the volume rtio of the retion mixture reltive to the vil n 'et the phse seletivity of the produtD presumly due to hnges in pressureF nintentionl evportion my lso 'et the onentrtionF wost prtiipnts used retion vessels with volumes of PH!QH mlD IS ut SH mlEvil ws lso used in one instneF pinllyD the tul temperture of the retion my vry depending on the heting soureD temperture grdientsD nd lirtion nd this ould ontriute to the devition in resultsF en intriguing onept sometimes invoked to explin disrepnies in synthesis is iE dentl seedingF sf mteril from previous syntheses is present in the lD they might t s rystllistion seeds nd diret the synthesis towrds prtiulr polymorphF en extreme exmple ours in soElled disppering polymorphismD where synthesis relily gives rise to prtiulr polymorphD ut suddenly"upon the identl introdution of seeds of more stle form"fils to produe the initil polymorph in fvour of the more stle oneF his prolem is well doumented in phrmeutil reserhD with ritonvir eing highE pro(le exmpleF 54 eeding n in)uene the retion outomes of wyps"nd hs indeed een suggested s method of direting the synthesis 55 "nd my lso ply role in the reproduiility issuesF his study lso rises questions out the postEsyntheti rgl tivtion of wypsF hile therml tivtion or superritil gy 2 Edrying my e more ommon methods for removing pore ontentD 37,56 the use of dilute rgl is neessry for the removl of oordinted modE ultorsF 37 he hnges to the h ptterns following tivtion n e explined y the removl of pore ontent or the deomposition of unstle intermeditesF his n id the distintion of rystlline wyps from intermedites with prtil rystllinityD s the ltter re less stle towrds tivtionF vess rtionlisle hnges re oserved in the qe tres fter tivtion isD where the deomposition eomes more grdul nd shifts to lower temperturesF peultivelyD this ould indite hnges to the oordintion or the onding"s the luster!linker onds re presumly the wekest link"nd n inresed spred of lol environmentsF his would men tht the frmework ollpse of wyps with pore ontent is delyed until the pores re emptyD wheres they re lredy empty in the tivted wypsD thus the onset of pore ollpse ours erlierF hile some studies on the hemil hnges indued y tivtion existD 57 further explortion of the e'et of tivtionD IT prtiulrly using lol proes would e illumintingF glosely relted to tivtion is the hllenge of hrterising defets in r!porphyrin wypsF vike for the iy fmilyD defets in the form of devitions from the idel stoiE hiometry re known in r!porphyrin systemsF qe gives n indiret mesure of the linkerGluster rtio nd hene the frtion of missing linkersD lthough the preision of qe vriesF 60 roweverD this ssumes tht missing linkers re the only type of defet presentD whih my not e trueF wissingEluster defets 58 hve een suggested to e the dominnt type of defets in rhetypil iyETTD nd n e deteted y h y virtue of their @prE tilA orderF 59 gonverselyD disordered luster vnies re di0ult to oserveD ut the high linkerGluster rtio found y qe for some smples here my point towrds suh defetsF vikewiseD the linkerGluster rtio osionlly inreses following tivtionD whih ould imE ply the removl of r IV "lone or s prt of lusterF his motivtes future studies into the role of tivtion nd defetivityF pinllyD it is worth speulting out the ompositionl ftors of prtiulr wyp system tht re onduive to unrelile syntheti outomesF he luster oordintion prefE erene is lerly keyX the r 6 @yrA 4 y 4 luster n vry its oordintion from R to IPD leding to welth of ville topologiesF yrienttionl order of the lusterD nd the ility to support vrious inding modes of the linker 17 my lso ply roleF he linker is lso releE vntD s wyps sed on r 6 @yrA 4 y 4 nd tetrkis@REroxyphenylApyrene lignds only form scu nd csq topologiesF 61,62 his ould e due to the lower symmetry of pyrene reltive to porphyrinD preventing the formtion of ui topologiesF reneD the syntheti reliility of prtiulr wyp system is in)uened y topologil ftorsD ut hemistry nd preferene of the uilding loks my lso e implitedF IU pigure RX he min results of the studyD inluding the verge phse frtion of trget mteril per smple for rude @lkA nd tivted @orngeA smplesD nd the numer of phseEpure smples otined of the trget wyp out of the ten synthesised smplesX one for gxEPPP nd three for gxEPPRF he disordered dgxEPPR is treted s equivlent to the linkerEordered gxEPPRF he results only onsider the rystlline prt of the smplesF